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The use of lithium metal either in an anode or anode-free configuration is envisaged as the most promising way to boost the energy density of the current lithium-ion battery system. Nevertheless, t...

Rechargeable calcium batteries have attracted increasing attention as promising multivalent ion battery systems due to the high abundance of calcium. However, the development has been hampered by the lack of suitable cathodes to accommodate the large and divalent Ca2+ ions at a high redox potential with sufficiently fast ionic conduction. Herein, we report a new intercalation host which presents 500 cycles with a capacity retention of 90% and a remarkable power capability at ~3.2 V (vs. Ca/Ca2+) in a calcium battery. The cathode material derived from Na0.5VPO4.8F0.7 is demonstrated to reversibly accommodate a large amount of Ca2+ ions, forming a series of CaxNa0.5VPO4.8F0.7 (0, Rechargeable calcium batteries are promising multivalent battery systems but the lack of suitable electrodes hampers their development. Here the authors report a cathode derived from polyanion framework that demonstrates uncommonly stable and fast intercalation behaviours of calcium ions.

The key challenges in all-solid-state batteries (ASSBs) are establishing and maintaining perfect physical contact between rigid components for facile interfacial charge transfer, particularly betwe...

Although layered-type cathode materials for lithium-ion batteries (LIBs) have received great attention due to their large gravimetric energy density, those for potassium rechargeable batteries (PRBs) just deliver small and limited energy density due to the large structural change and phase transition during de/intercalation of K+ ions with a large ionic size. Thus, a new approach is required for achieving high energy densities. A cathode material that results in ultrahigh energy density for potassium rechargeable batteries (PRBs) based on the conversion reaction of K–SO4–Cu in the system was developed. To maximize the electrochemical performance, a copper-sulfate/carbon nanocomposite (hereafter denoted as N-CSO/C) was prepared using a simple high-energy ball-milling process. At a current density of 12 mA g−1, the conversion reaction of K–SO4–Cu in the PRB system resulted in a specific capacity of ∼240 mA h g−1 with an average operating voltage of ∼2.8 V (vs. K+/K). This capacity and the resulting energy density are larger than those of other cathode materials for PRBs reported to date. After 200 cycles at 360 mA g−1, N-CSO/C retained ∼70% of the initial capacity. The overall reversible reaction mechanism of K–SO4–Cu in N-CSO/C in the PRB system was investigated through combined studies using first-principles calculation and various experimental techniques.

Lithium metal batteries (LMBs) are considered the most promising next-generation battery system because of their high energy density and safety. Significant research effort has been devoted to developing more stable and energy-dense LMBs than the state-of-the-art Li-ion batteries. However, the LMB performance remains unsatisfactory for commercialization, primarily owing to the inability of solid electrolytes to block Li dendrite propagation. Herein, we demonstrate highly stable LMB employing garnet-type oxide electrolyte by introducing a carbon-based interlayer with careful interface engineering. We theoretically and experimentally demonstrate that our design effectively regulated Li deposition away from the solid electrolyte, preventing dendrite penetration. We further demonstrated that the interface condition between the interlayer and solid electrolyte is critical and present an effective strategy to achieve an optimal interface. Overall, our garnet-type oxide-based LMB exhibited a high energy density of ~ 680 Wh/L for over 800 cycles at room temperature without using external pressure.

Compared to the tetragonal phase, the cubic phase polymorphism of garnet-type solid electrolytes (Li7La3M2O12) has attracted considerable interest for all-solid-state batteries owing to their high ionic conductivity. Herein, we successfully synthesized a cubic-phase garnet without vacancy formation (Li = 7.0) by applying multicomponent (Hf, Sn, Sc, and Ta) substitutions in the Zr site, considering defect formation energy, site-exchange energy, and charge balance. The entropy-driven stabilization allowed access to the hidden chemical space in cubic-phase garnet (Li > 6.6), and signified the feasibility of low-temperature synthesis as the nucleation temperature of cubic phase decreased from 750 to 400 ℃ in the solid-state reaction. Specifically, Li = 7.0 cubic-phase garnet-type solid electrolyte exhibited superior reduction stability against lithium metal compared to that with low lithium contents (Li = 6.6) and identical atomic species, which further demonstrated the long-term cycle operational stability of such solid-state batteries. The present findings exemplified the superior reduction stability of the cubic-phase garnet with higher chemical potential of lithium to design solid electrolytes.

The development of a cathode for solid-state lithium-oxygen batteries has been hindered in practice by a low capacity and limited cycle life despite their potential for high energy density. Here, a previously unexplored strategy is proposed wherein the cathode delivers a specific capacity of 200 milliampere hour per gram over 665 discharge/charge cycles, while existing cathodes achieve only ~50 milliampere hour per gram and ~100 cycles. A highly conductive ruthenium-based composite is designed as a carbon-free cathode by first-principles calculations to avoid the degradation associated with carbonaceous materials, implying an improvement in stability during the electrochemical cycling. In addition, water vapor is added into the main oxygen gas as an additive to change the discharge product from growth-restricted lithium peroxide to easily grown lithium hydroxide, resulting in a notable increase in capacity. Thus, the proposed strategy is effective for developing reversible solid-state lithium-oxygen batteries with high energy density.

Despite the high energy density of lithium-rich layered-oxide electrodes, their real-world implementation in batteries is hindered by the substantial voltage decay on cycling. This voltage decay is widely accepted to mainly originate from progressive structural rearrangements involving irreversible transition-metal migration. As prevention of this spontaneous cation migration has proven difficult, a paradigm shift toward management of its reversibility is needed. Herein, we demonstrate that the reversibility of the cation migration of lithium-rich nickel manganese oxides can be remarkably improved by altering the oxygen stacking sequences in the layered structure and thereby dramatically reducing the voltage decay. The preeminent intra-cycle reversibility of the cation migration is experimentally visualized, and first-principles calculations reveal that an O2-type structure restricts the movements of transition metals within the Li layer, which effectively streamlines the returning migration path of the transition metals. Furthermore, we propose that the enhanced reversibility mitigates the asymmetry of the anionic redox in conventional lithium-rich electrodes, promoting the high-potential anionic reduction, thereby reducing the subsequent voltage hysteresis. Our findings demonstrate that regulating the reversibility of the cation migration is a practical strategy to reduce voltage decay and hysteresis in lithium-rich layered materials.

Lithium-rich layered oxides (LLOs) are considered promising cathode materials for lithium-ion batteries because of their high reversible capacity, which is attributed to the exploitation of the novel anionic redox in addition to the conventional cationic redox process. Transition metal (TM) migration, which is known to be the main cause of the voltage decay in LLOs, is now understood to also be the critical factor triggering anionic redox, although this origin is still under debate. A better understanding of the specific TM migration behavior and its effect during charge/discharge would thus enable further development of this class of materials. Herein, we demonstrate that the unique TM migration during charge/discharge significantly alters the lithium diffusion mechanism/kinetics of LLO cathodes. We present clear evidence of the much more sluggish lithium diffusion occurring during discharge (lithiation) than during charge (de-lithiation), which contrasts with the traditional lithium diffusion model based on simple topotactic lithium intercalation/deintercalation in the layered framework. The reversible but asymmetric TM migration in the structure, which originates from the non-equivalent local environments around the TM during the charge and discharge processes, is shown to affect the lithium mobility. This correlation between TM migration and lithium mobility led us to propose a new lithium diffusion model for layered structures and suggests the importance of considering TM migration in designing new LLO cathode materials.

Organic redox compounds are potential substitutes for transition-metal-oxide electrode materials in rechargeable batteries because of their low cost, minimal environmental footprint, and chemical diversity. However, their inherently low electrical conductivity and high solubility in organic solvents are serious impediments to achieving performance comparable to that of currently used inorganic-based electrode materials. Herein, we report organic charge-transfer complexes as a novel class of electrode materials with intrinsically high electrical conductivity and low solubility that can potentially overcome the chronic drawbacks associated with organic electrodes. The formation of the charge-transfer complexes, phenazine–7,7,8,8-tetracyanoquinodimethane and dibenzo-1,4-dioxin–7,7,8,8-tetracyanoquinodimethane, via a room-temperature process leads to enhancement in the electrical conductivity and reduction in the dissolution resulting in the high power and cycle performances that far outperform those of each single-moiety counterpart. This finding demonstrates the general applicability of the charge-transfer complex to simultaneously improve the electrical conductivity and mitigate the shortcomings of existing single-moiety-based organic electrode materials, and opens up an uncharted pathway toward the development of high-performance organic electrode materials via the exploration of various combinations of donor–acceptor monomers with different stoichiometry.

Co-intercalation reactions make graphite as promising anodes for sodium ion batteries, however, the high redox potentials significantly lower the energy density. Herein, we investigate the factors that influence the co-intercalation potential of graphite and find that the tuning of the voltage as large as 0.38 V is achievable by adjusting the relative stability of ternary graphite intercalation compounds and the solvent activity in electrolytes. The feasibility of graphite anode in sodium ion batteries is confirmed in conjunction with Na1.5VPO4.8F0.7 cathodes by using the optimal electrolyte. The sodium ion battery delivers an improved voltage of 3.1 V, a high power density of 3863 W kg−1both electrodes, negligible temperature dependency of energy/power densities and an extremely low capacity fading rate of 0.007% per cycle over 1000 cycles, which are among the best thus far reported for sodium ion full cells, making it a competitive choice in large-scale energy storage systems., Graphite is a promising anode material for sodium-ion batteries but suffers from the high co-intercalation potential. Here, the authors examine the factors influencing this potential and tailor the stability of graphite intercalation compound, realizing high energy and power densities.

The popularization of electric vehicles and the increasing use of electronic devices highlight the importance of fast charging technology. The charging process of lithium secondary battery is basically limited by a series of processes on the anode side, which include desolvation of lithium ions as well as lithium diffusion through SEI and the anode material. These series of reactions are kinetically sluggish, leading to insufficient power density. Therefore, to unravel this problem, we need to either accelerate each step or skip over some of the steps to make the whole charging process shorter. A solvated ion cointercalation into graphite has turned out to successfully exclude both desolvation of lithium ions and SEI film formation to achieve high kinetics with graphite. Herein, the solvated ion cointercalation into MoS2 demonstrated that it can help to remove desolvation of alkali ions as well as SEI formation, and thereby ultrahigh kinetics and long-term cyclability are attained by the characteristic ps...

The development of a cathode for solid-state lithium-oxygen batteries has been hindered in practice by a low capacity and limited cycle life despite their potential for high energy density. Here, a previously unexplored strategy is proposed wherein the cathode delivers a specific capacity of 200 milliampere hour per gram over 665 discharge/charge cycles, while existing cathodes achieve only ~50 milliampere hour per gram and ~100 cycles. A highly conductive mixed ionic-electronic conductors (MIECs) are designed as a carbon-free cathode by first-principles calculations with a density functional theory (DFT) and nudged elastic band (NEB) to avoid the degradation associated with carbonaceous materials, implying an improvement in stability during the electrochemical cycling [1]. In addition, water vapor is added into the main oxygen gas as an additive to change the discharge product from growth-restricted lithium peroxide to easily grown lithium hydroxide, resulting in a significant increase in capacity [2]. Thus, the proposed strategy is effective for developing reversible solid-state lithium-oxygen batteries with high energy density. We will discuss on the systematic materials design and their electrochemical properties for solid-state lithium-oxygen batteries at the meeting. References [1] Sang Bok Ma et al., Advanced Energy Materials, 10 (2020) 2001767. [2] Mokwon Kimet al., Science Advances, in press. Figure 1

Increasing demands for performance beyond the limit of current lithium ion batteries for higher energy densities have rejuvenated research using lithium metal as an anode. However, commercial implementation has still been hampered due to safety issues. Herein, we introduce a lithium rechargeable battery system with an auxiliary electrode that can detect the potential signs of an internal short-circuit and simultaneously prevent cell failure by inhibiting further dendritic growth of lithium metal. Based on this working principle, we provide guidelines for an auxiliary electrode design and demonstrate that it can act as both a safety sensor and a lithium scavenger. Finally, we show that our in-house designed cell, using a flexible and self-standing auxiliary electrode, can effectively alert the danger of a short circuit in real-time without additional dendrite growth. We expect that this finding will open up unexplored opportunities utilizing various auxiliary electrode chemistries for safe rechargeable lithium metal batteries.

Demand for an effective strategy for exfoliating layered materials into flakes without perturbing their intrinsic structure is growing. Herein, we introduce an effective fabrication method of large-sized non-oxidized graphene flakes (NOGFs) as a representative example of a general strategy using spontaneous insertion of exfoliating medium into a layered material. We fabricated a ternary graphite intercalation compound (t-GIC) with stoichiometry of KC24(THF)2, and analyzed its morphology and electronic structure through experimental and computational approach. Interactions between the t-GIC and aprotic organic solvents with different polarities were investigated, where a unique swelling behavior was observed with dimethyl sulfoxide (DMSO). Based on the analysis of the phenomena, we demonstrate facile exfoliation of the t-GIC in polyvinyl pyrrolidone (PVP)-DMSO solution for fabrication of highly crystalline and large-sized NOGFs. The lateral size of the NOGFs ranges over 30 μm, while the 98% having thickness below 10 layers. The NOGF film exhibits supreme electrical conductivity of 3.36 × 105 S/m, which is, to our best knowledge, the highest value for a thin conductive film made of graphene flakes.

Metallic lithium (Li) is a promising anode candidate for high-energy-density rechargeable batteries because of its low redox potential and high theoretical capacity. However, its practical application is not imminent because of issues related to the dendritic growth of Li metal with repeated battery operation, which presents a serious safety concern. Herein, various aspects of the electrochemical deposition and stripping of Li metal are investigated with consideration of the reaction rate/current density, electrode morphology, and solid electrolyte interphase (SEI) layer properties to understand the conditions inducing abnormal Li growth. It is demonstrated that the irregular (i.e., filamentary or dendritic) growth of Li metal mostly originates from local perturbation of the surface current density, which stems from surface irregularities arising from the morphology, defective nature of the SEI, and relative asymmetry in the deposition/stripping rates. Importantly, we find that the use of a stripping rate...

Defects in crystals alter the intrinsic nature of pristine materials including their electronic/crystalline structure and charge-transport characteristics. The ionic transport properties of solid-state ionic conductors, in particular, are profoundly affected by their defect structure. Nevertheless, a fundamental understanding of the defect structure of one of the most extensively studied lithium superionic conductors, Li10GeP2S12, remains elusive because of the complexity of the structure; the effects of defects on lithium diffusion and the potential to control defects by varying synthetic conditions also remain unknown. Herein, we report, for the first time, a comprehensive first-principles study on native defects in Li10GeP2S12 and their effect on lithium diffusion. We provide the complete defect profile of Li10GeP2S12 and identify major defects that are easily formed regardless of the chemical environment while the presence of path-blocking defects is sensitively dependent on the synthetic conditions. ...

We introduce Na3V(PO4)2 as a new cathode material for Na-ion batteries for the first time. The structure of Na3V(PO4)2 was determined using X-ray diffraction and Rietveld refinement, and its high water stability was clearly demonstrated. The redox potential of Na3V(PO4)2 (∼3.5 V vs Na/Na+) was shown to be sufficiently high to prevent the side reaction with water (Na extraction and water insertion), ensuring its water stability in ambient air. Na3V(PO4)2 also exhibited outstanding power capability, with ∼79% of the theoretical capacity being delivered at 15C. First-principles calculation combined with electrochemical experiments linked this high power capability to the low activation barrier (∼433 meV) for the well-interconnected two-dimensional Na diffusion pathway. Moreover, outstanding cyclability of Na3V(PO4)2 (∼70% retention of the initial capacity after 200 cycles) was achieved at a reasonably fast current rate of 1C.

Layered crystal structures are some of the most intensively studied intercalation hosts for guest ion insertion. For Mg insertion, layered transition metal sulfides or selenides have been used for reversible Mg intercalation; however, far less intercalation hosts have been found for layered oxides most likely because of the strong interaction between Mg 2+ and the oxide host. Here, we demonstrate that layered Li x Ni 0.5 Co 0.2 Mn 0.3 O 2 (NCM523), which is an important commercial electrode for Li-ion batteries but has been regarded as electrochemically inactive in rechargeable Mg batteries, can function as a reversible host for Mg 2+ if water opens up the layers and screens the electrostatic interaction between Mg 2+ and the host. Upon the formation of water-intercalated NCM523, the discharge capacity dramatically increases utilizing the multi-redox reaction of Ni 2+ /Ni 3+ /Ni 4+ , which exhibits an average voltage of ∼3.1 V ( vs. Mg/Mg 2+ ) in rechargeable Mg batteries with an energy density of 589 Wh kg −1 in the first discharge.

Increasing demands for advanced lithium batteries with higher energy density have resurrected the use of lithium metal as an anode, whose practical implementation has still been restricted, because of its intrinsic problems originating from the high reactivity of elemental lithium metal. Herein, we explore a facile strategy of doping gas phase into electrolyte to stabilize lithium metal and suppress the selective lithium growth through the formation of stable and homogeneous solid electrolyte interphase (SEI) layer. We find that the sulfur dioxide gas additive doped in electrolyte significantly improves both chemical and electrochemical stability of lithium metal electrodes. It is demonstrated that the cycle stability of the lithium cells can be remarkably prolonged, because of the compact and homogeneous SEI layers consisting of Li–S–O reduction products formed on the lithium metal surface. Simulations on the lithium metal growth process suggested the homogeneity of the protective layer induced by the ga...

Here, we introduce Na3V(PO3)3N as a novel 4V-class and zero-strain cathode material for Na-ion batteries. Structural analysis based on a combination of neutron and X-ray diffraction (XRD) reveals that the Na3V(PO3)3N crystal contains three-dimensional channels that are suitable for facile Na diffusion. The Na (de)intercalation is observed to occur at ∼4 V vs Na/Na+ in the Na cell via the V3+/V4+ redox reaction with ∼67% retention of the initial capacity after over 3000 cycles. The remarkable cycle stability is attributed to the near-zero volume change (∼0.24%) and unique centrosymmetric distortion that occurs during a cycle despite the large ionic size of Na ions for (de)intercalation, as demonstrated by ex situ XRD analysis and first-principles calculations. We also demonstrate that the Na3V(PO3)3N electrode can display outstanding power capability with ∼84% of the theoretical capacity retained at 10C, even though the particle sizes are on the micrometer scale (>5 μm), which is attributed to its intrinsi...

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li+/Na+ substitution during solvothermal ion-exchange synthesis of LixNa1.5–xVOPO4F0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na+ by Li+, leading to peculiar Na+/Li+/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phas...

A highly active and stable non-Pt electrocatalyst for hydrogen production has been pursued for a long time as an inexpensive alternative to Pt-based catalysts. Herein, we report a simple and effective approach to prepare high-performance iron phosphide (FeP) nanoparticle electrocatalysts using iron oxide nanoparticles as a precursor. A single-step heating procedure of polydopamine-coated iron oxide nanoparticles leads to both carbonization of polydopamine coating to the carbon shell and phosphidation of iron oxide to FeP, simultaneously. Carbon-shell-coated FeP nanoparticles show a low overpotential of 71 mV at 10 mA cm–2, which is comparable to that of a commercial Pt catalyst, and remarkable long-term durability under acidic conditions for up to 10 000 cycles with negligible activity loss. The effect of carbon shell protection was investigated both theoretically and experimentally. A density functional theory reveals that deterioration of catalytic activity of FeP is caused by surface oxidation. Extende...

The key challenge in all-solid-state batteries (ASSBs) is establishing perfect physical contact between rigid components for facile interfacial charge transfer, especially between the solid electrolyte and cathode. Here, we introduce a new class of shapeable inorganic-based solid electrolytes with a liquid-like sublattice that can form intimate contact with the rigid cathode. The electrolyte exhibits extraordinary clay-like mechanical properties (storage and loss moduli < 1 MPa) at room temperature, high lithium ion conductivity (3.4 mS cm-1), and a glass transition below -50 ℃. The unique mechanical features provide liquid-like penetration into the porous cathode and ionic conduction paths for all cathode particles, delivering a high energy density. We propose a design principle that the complex anion formation including Ga, F and a different halogen can induce the clay-like features. Our findings provide new opportunities in the search for solid electrolytes and suggest a new approach for resolving the issues caused by the solid electrolyte–cathode interface in ASSBs.

The development of long-lasting and low-cost rechargeable batteries lies at the heart of the success of large-scale energy storage systems for various applications. Here, we introduce Fe- and Mn-based Na rechargeable battery cathodes that can stably cycle more than 3000 times. The new cathode is based on the solid-solution phases of Na4MnxFe3–x(PO4)2(P2O7) (x = 1 or 2) that we successfully synthesized for the first time. Electrochemical analysis and ex situ structural investigation reveal that the electrodes operate via a one-phase reaction upon charging and discharging with a remarkably low volume change of 2.1% for Na4MnFe2(PO4)(P2O7), which is one of the lowest values among Na battery cathodes reported thus far. With merits including an open framework structure and a small volume change, a stable cycle performance up to 3000 cycles can be achieved at 1C and room temperature, and almost 70% of the capacity at C/20 can be obtained at 20C. We believe that these materials are strong competitors for large-s...

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Conversion reaction electrodes offer a high specific capacity in rechargeable batteries by utilizing wider valence states of transition metals than conventional intercalation-based electrodes and have thus been intensively studied in recent years as potential electrode materials for high-energy-density rechargeable batteries. However, several issues related to conversion reactions remain poorly understood, including the polarization or hysteresis during charge/discharge processes. Herein, Co3O4in Na cells is taken as an example to understand the aforementioned properties. The large hysteresis in charge/discharge profiles is revealed to be due to different electrochemical reaction paths associated with respective charge and discharge processes, which is attributed to the mobility gap among inter-diffusing species in a metal oxide compound during de/sodiation. Furthermore, a Co3O4–graphene nanoplatelet hybrid material is demonstrated to be a promising anode for Na rechargeable batteries, delivering a capacity of 756 mAh g−1with a good reversibility and an energy density of 96 Wh kg−1(based on the total electrode weight) when combined with a recently reported Na4Fe3(PO4)2(P2O7) cathode.

Lithium iron phosphate (LFP) has attracted tremendous attention as an electrode material for next-generation lithium-rechargeable battery systems due to the use of low-cost iron and its electrochemical stability. While the lithium diffusion in LFP, the essential property in battery operation, is relatively fast due to the one-dimensional tunnel present in the olivine crystal, the tunnel is inherently vulnerable to the presence of FeLi anti-site defects (Fe ions in Li ion sites), if any, that block the lithium diffusion and lead to inferior performance. Herein, we demonstrate that the kinetic issue arising from the FeLi defects in LFP can be completely eliminated in lithium-excess olivine LFP. The presence of an excess amount of lithium in the Fe ion sites (LiFe) energetically destabilizes the FeLi-related defects, resulting in reducing the amount of Fe defects in the tunnel. Moreover, we observe that the spinodal decomposition barrier is notably reduced in lithium-excess olivine LFP. The presence of LiFe and the absence of FeLi in lithium-excess olivine LFP additionally induce faster kinetics, resulting in an enhanced rate capability and a significantly reduced memory effect. The lithium-excess concept in the electrode crystal brings up unexpected properties for the pristine crystal and offers a novel and interesting approach to enhance the diffusivity and open up additional diffusion paths in solid-state ionic conductors.

© 2016 Royal Society of Chemistry. Here, we demonstrate that graphite can serve as a versatile electrode for various rechargeable battery types by reversibly accommodating solvated alkali ions (such as K, Na, and Li) through co-intercalation in its galleries. The co-intercalation of alkali ions is observed to occur via staging reactions. Notably, their insertion behaviors, including their specific capacity, are remarkably similar regardless of the alkali ion species despite the different solubility limits of K, Na, and Li ions in graphite. Nevertheless, the insertion potentials of the solvated alkali ions differ from each other and are observed to be correlated with the interlayer distance in the intercalated graphite gallery.

Li–oxygen and Na–oxygen batteries are some of the most promising next-generation battery systems because of their high energy densities. Despite the chemical similarity of Li and Na, the two systems exhibit distinct characteristics, especially the typically higher charging overpotential observed in Li–oxygen batteries. In previous theoretical and experimental studies, this higher charging overpotential was attributed to factors such as the sluggish oxygen evolution or poor transport property of the discharge product of the Li–oxygen cell; however, a general understanding of the interplay between the discharge products and overpotential remains elusive. Here, we investigated the charging mechanisms with respect to the oxygen evolution reaction (OER) kinetics, charge-carrier conductivity, and dissolution property of various discharge products reported in Li–oxygen and Na–oxygen cells. The OER kinetics were generally faster for superoxides (i.e., LiO2 and NaO2) than for peroxides (i.e., Li2O2 and Na2O2). The...

Demand on the practical synthetic approach to the high performance electrocatalyst is rapidly increasing for fuel cell commercialization. Here we present a synthesis of highly durable and active intermetallic ordered face-centered tetragonal (fct)-PtFe nanoparticles (NPs) coated with a "dual purpose" N-doped carbon shell. Ordered fct-PtFe NPs with the size of only a few nanometers are obtained by thermal annealing of polydopamine-coated PtFe NPs, and the N-doped carbon shell that is in situ formed from dopamine coating could effectively prevent the coalescence of NPs. This carbon shell also protects the NPs from detachment and agglomeration as well as dissolution throughout the harsh fuel cell operating conditions. By controlling the thickness of the shell below 1 nm, we achieved excellent protection of the NPs as well as high catalytic activity, as the thin carbon shell is highly permeable for the reactant molecules. Our ordered fct-PtFe/C nanocatalyst coated with an N-doped carbon shell shows 11.4 times-higher mass activity and 10.5 times-higher specific activity than commercial Pt/C catalyst. Moreover, we accomplished the long-term stability in membrane electrode assembly (MEA) for 100 h without significant activity loss. From in situ XANES, EDS, and first-principles calculations, we confirmed that an ordered fct-PtFe structure is critical for the long-term stability of our nanocatalyst. This strategy utilizing an N-doped carbon shell for obtaining a small ordered-fct PtFe nanocatalyst as well as protecting the catalyst during fuel cell cycling is expected to open a new simple and effective route for the commercialization of fuel cells.

The present work introduces a new intercalation host for the Na ions, Nb2O5, and proposes that a mesoporous Nb2O5/carbon composite can function as a promising sodium insertion material. The highly ordered mesoporous Nb2O5/carbon electrode, synthesized using a block copolymer-assisted one-pot method, demonstrated not only a stable cycle life, but also outstanding rate capability. The excellent Na storage properties of the Nb2O5/carbon electrode were due to the uniquely ordered mesoporous nanostructure and in situ carbon formation whose configuration provided a large electrode–electrolyte interface area and enhanced Na ion and electron transport. Ex situ analyses revealed that Nb2O5 stores Na ions through Na de/intercalation reactions combined with surface capacitive reactions, after the activation process during the first sodiation.

We investigate the mechanism of the intercalation-aided exfoliation of graphite using van der Waals force-corrected density functional theory (DFT) calculations. From a comparative study on various intercalation systems, we find that, depending on the intercalant species, the exfoliation energies vary significantly, not only due to the size of intercalants but also due to interactions with the host graphite. While it is generally perceived that an expanded interlayer distance with intercalants weakens the binding between graphene layers, as the van der Waals forces decrease, the calculations reveal that the intercalation of electronegative or electropositive intercalants (e.g., Li, K, F, Cl, and Br) result in a 1.5–5-fold higher exfoliation energy than pristine graphite due to additional binding forces from charge transfer between intercalants and graphene layers. Furthermore, we demonstrate that this additional binding force could be manipulated with cointercalation or neutral intercalants, which hints a...

Graphene flakes (GFs) with minimized defects and oxidation ratios are incorporated into polyethylene (PE) to enhance the moisture barrier. GFs produced involving solvothermal intercalation show extremely low oxidation rates (3.17%), and are noncovalently functionalized in situ, inducing strong hydrophobicity. The fabricated composite possesses the best moisture barrier performance reported for a polymer-graphene composite.