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Cobalt substitution for manganese sites in Na0.44MnO2 initiates a dynamic structural evolution process, yielding a composite cathode material comprising intergrown P2 and P3 phases. The novel P2/P3 composite cathode exhibits a reversible phase transition process during Na+ extraction/insertion, showcasing its attractive battery performance in sodium-ion batteries. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (NIBs) have emerged as a promising alternative to commercial lithium‐ion batteries (LIBs) due to the similar properties of the Li and Na elements as well as the abundance and accessibility of Na resources. Most of the current research has been focused on the half‐cell system (using Na metal as the counter electrode) to evaluate the performance of the cathode/anode/electrolyte. The relationship between the performance achieved in half cells and that obtained in full cells, however, has been neglected in much of this research. Additionally, the trade‐off in the relationship between electrochemical performance and cost needs to be given more consideration. Therefore, systematic and comprehensive insights into the research status and key issues for the full‐cell system need to be gained to advance its commercialization. Consequently, this review evaluates the recent progress based on various cathodes and highlights the most significant challenges for full cells. Several strategies have also been proposed to enhance the electrochemical performance of NIBs, including designing electrode materials, optimizing electrolytes, sodium compensation, and so forth. Finally, perspectives and outlooks are provided to guide future research on sodium‐ion full cells. [ABSTRACT FROM AUTHOR]

Hydrogen‐bonded organic frameworks (HOFs) are considered as potential choice for future energy storage systems due to their adjustable chemistry, environment friendliness, and cost‐effectiveness. In this study, structurally stabilized and aldehyde‐tuned hydrogen‐bonded organic frameworks (HOFs‐8) are designed and prepared to contain arrayed electronegative sites for sodium‐ion storage. Benefitting from the flexible hydrogen bond and unique structural symmetry, HOFs‐8 can achieve efficient utilization of the active sites and fast transport of sodium ions and electrons. The HOFs‐8 electrode exhibits an impressive lifespan of 5000 cycles at 3.66 A g−1 (20 C). In situ Fourier Transform infrared spectroscopy (in situ FT‐IR) and ex situ X‐ray Photoelectron Spectroscopy (ex situ XPS) analyses are performed to illustrate the mechanism of sodium‐ion storage involving aldehyde‐tuned C═O. Additionally, flexible hydrogen bonds in HOFs materials with unique structural symmetries are investigated to elucidate the mechanism of hydrogen bonding for improving their electrochemical properties. Density functional theory (DFT) simulations verified that HOFs‐8 has excellent Na+ diffusion kinetics, enabling it to demonstrate outstanding rate capability. This work offers insight into the design of new electrodes and improved HOFs, which are expected to have tremendous potential in energy storage systems. [ABSTRACT FROM AUTHOR]

Zn deposition with a surface‐preferred (002) crystal plane has attracted extensive attention due to its inhibited dendrite growth and side reactions. However, the nucleation and growth of the Zn(002) crystal plane are closely related to the interfacial properties. Herein, oriented growth of Zn(002) crystal plane is realized on Ag‐modified surface that is directly visualized by in situ atomic force microscopy. A solid solution HCP‐Zn (~1.10 at. % solubility of Ag, 30 °C) is formed on the Ag coated Zn foil (Zn@Ag) and possesses the same crystal structure as Zn to reduce its nucleation barrier caused by their lattice mismatch. It merits oriented Zn deposition and corrosion‐resistant surface, and presents long cycling stability in symmetric cells and full cells coupled with V2O5 cathode. This work provides insights into interfacial regulation of Zn anodes for high‐performance aqueous zinc metal batteries. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) with wide operating temperature are regarded as promising candidates for large‐scale energy storage systems. However, SIBs operating under elevated temperature aggravate the electrolyte decomposition with unstable cathode‐electrolyte interphase (CEI), causing a rapid capacity degradation. Herein, anion receptor tris(pentafluorophenyl)borane (TPFPB) is selected as electrolyte additive to construct robust NaF‐rich CEI. The strong interactions between anion and TPFPB via the electron‐deficient boron atoms weaken ClO4− solvation and promote the coordination capability between solvents and Na+ cations, demonstrating greatly improved oxidative stability. Na3V2(PO4)3 cathode in TPFPB‐containing electrolyte delivers long‐term stability with a capacity retention of 86.9% after 100 cycles at a high cut‐off voltage of 4.2 V (vs. Na+/Na) and a high temperature of 60 °C. Besides, TPFPB also works well with enhanced performance over a temperature range from −30 to 60 °C. This study proposes a prospective method by manipulating the solvation chemistry for constructing high‐temperature rechargeable SIBs. [ABSTRACT FROM AUTHOR]

As a class of promising cathodes in the field of large-scale power storage systems especially for alkali-metal-ion batteries (MIBs), Prussian blue (PB) and its analogues (PBAs) have received wide research attention due to their open framework, high theoretical specific capacity, and simple synthesis method. For large-scale applications, cathode materials with low-cost and long cycle life are preferred. However, only a few of the review papers have concentrated on the detailed analysis of low-cost PBAs, including Fe-based and Mn-based PBAs, which also show excellent electrochemical performance. This review aims to first provide an all-sided understanding of low-cost PBAs in terms of their application and recent progress in MIBs. Then, the major challenges such as inferior electrochemical properties of low-cost PBAs are discussed. Meanwhile, we provide feasible strategies to prepare PBA electrodes with advanced electrochemical performance. Finally, we present some personal perspectives and guidance for future research, aiming to narrow the gap between laboratory investigation and practical application. [ABSTRACT FROM AUTHOR]

Prussian blue analogues (PBAs) have been regarded as promising cathode materials for alkali‐ion batteries owing to their high theoretical energy density and low cost. However, the high water and vacancy content of PBAs lower their energy density and bring safety issues, impeding their large‐scale application. Herein, a facile "potassium‐ions assisted" strategy is proposed to synthesize highly crystallized PBAs. By manipulating the dominant crystal plane and suppressing vacancies, the as‐prepared PBAs exhibit increased redox potential resulting in high energy density up to ≈450 Wh kg−1, which is at the same level of the well‐known LiFePO4 cathodes for lithium‐ion batteries. Remarkably, unconventional highly‐reversible phase evolution and redox‐active pairs were identified by multiple in situ techniques for the first time. The preferred guest‐ion storage sites and migration mechanism were systematically analysed through theoretical calculations. We believe these results could inspire the design of safe with high energy density. [ABSTRACT FROM AUTHOR]

Hard carbon (HC) anodes have shown extraordinary promise for sodium‐ion batteries, but are limited to their poor initial coulombic efficiency (ICE) and low practical specific capacity due to the large amount of defects. These defects with oxygen containing groups cause irreversible sites for Na+ ions. Highly graphited carbon decreases defects, while potentially blocking diffusion paths of Na+ ions. Therefore, molecular‐level control of graphitization of hard carbon with open accessible channels for Na+ ions is key to achieve high‐performance hard carbon. Moreover, it is challenging to design a conventional method to obtain HCs with both high ICE and capacity. Herein, a universal strategy is developed as manganese ions‐assisted catalytic carbonization to precisely tune graphitization degree, eliminate defects, and maintain effective Na+ ions paths. The as‐prepared hard carbon has a high ICE of 92.05% and excellent cycling performance. Simultaneously, a sodium storage mechanism of "adsorption‐intercalation‐pore filling‐sodium cluster formation" is proposed, and a clear description given of the boundaries of the pore structure and the specific dynamic process of pore filling. [ABSTRACT FROM AUTHOR]

Prussian blue analogues (PBAs) have attracted extensive attention as cathode materials in sodium‐ion batteries (SIBs) due to their low cost, high theoretical capacity, and facile synthesis process. However, it is of great challenge to control the crystal vacancies and interstitial water formed during the aqueous co‐precipitation method, which are also the key factors in determining the electrochemical performance. Herein, an antioxidant and chelating agent co‐assisted non‐aqueous ball‐milling method to generate highly‐crystallized Na2‐xFe[Fe(CN)6]y with hollow structure is proposed by suppressing the speed and space of crystal growth. The as‐prepared Na2‐xFe[Fe(CN)6]y hollow nanospheres show low vacancies and interstitial water content, leading to a high sodium content. As a result, the Na‐rich Na1.51Fe[Fe(CN)6]0.87·1.83H2O hollow nanospheres exhibit a high initial Coulombic efficiency, excellent cycling stability, and rate performance via a highly reversible two‐phase transition reaction confirmed by in situ X‐ray diffraction. It delivers a specific capacity of 124.2 mAh g−1 at 17 mA g−1, presenting ultra‐high rate capability (84.1 mAh g−1 at 3400 mA g−1) and cycling stability (65.3% capacity retention after 1000 cycles at 170 mA g−1). Furthermore, the as‐reported non‐aqueous ball‐milling method could be regarded as a promising method for the scalable production of PBAs as cathode materials for high‐performance SIBs. [ABSTRACT FROM AUTHOR]

Binders as a bridge in electrodes can bring various components together thus guaranteeing the integrity of electrodes and electronic contact during battery cycling. In this review, we summarize the recent progress of traditional binders and novel binders in the different electrodes of SIBs. The challenges faced by binders in terms of bond strength, wettability, thermal stability, conductivity, cost, and environment are also discussed in details. Correspondingly, the designing principle and advanced strategies of future research on SIB binders are also provided. Moreover, a general conclusion and perspective on the development of binder design for SIBs in the future are presented. [ABSTRACT FROM AUTHOR]

Hard carbon (HC) is recognized as a promising anode material with outstanding electrochemical performance for alkali metal‐ion batteries including lithium‐ion batteries (LIBs), as well as their analogs sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs). Herein, a comprehensive review of the recent research is presented to interpret the challenges and opportunities for the applications of HC anodes. The ion storage mechanisms, materials design, and electrolyte optimizations for alkali metal‐ion batteries are illustrated in‐depth. HC is particularly promising as an anode material for SIBs. The solid‐electrolyte interphase, initial Coulombic efficiency, safety concerns, and all‐climate performances, which are vital for practical applications, are comprehensively discussed. Furthermore, commercial prototypes of SIBs based on HC anodes are extensively elaborated. The remaining challenges and research perspectives are provided, aiming to shed light on future research and early commercialization of HC‐based SIBs. [ABSTRACT FROM AUTHOR]

Aqueous zinc‐ion batteries (ZIBs) have triggered a great deal of scientific research and become a promising alternative for large‐scale energy storage applications, owing to the unique merits of high volumetric energy density, abundance of zinc resources, eco‐friendliness, and safety. The pace of progress of ZIB development, however, is hindered by their poor reversibility and sluggish kinetics, derived from the dissolution of active materials in aqueous electrolytes and the strong electrostatic interactions between Zn2+ and the cathode lattice. Herein, a vanadium oxide (V2O5‐x)/polyaniline (PANI‐V) superlattice structure is demonstrated as a model of superlattice structural engineering to overcome these weaknesses. In this superlattice, the PANI layer not only plays the role of a spacer to expand the V2O5‐x interlayer spacing but also serves as a conductive capacity contributor. Moreover, the PANI layer servers as structural stabilizer to restrain the dissolution of V2O5‐x active materials in aqueous electrolytes. In addition, it introduces an interface effect to modulate the charge distribution of the V2O5‐x monolayer, promoting Zn‐ion diffusion into the structure. Correspondingly, weakening the electrostatic interactions and supressing the active materials dissolution synergistically boosts the electrochemical performance for Zn‐ion storage. This work paves the way for the development/improvement of cathodes for aqueous zinc‐ion batteries. [ABSTRACT FROM AUTHOR]

Next‐generation sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs) are considered to be promising alternatives to replace current lithium‐ion batteries due to the high abundance of sodium and potassium resources. New energetic vanadium‐based compounds that undergoes multielectron reactions and demonstrate good sodium/potassium storage capability, provide new solutions for high‐performance SIBs/PIBs in terms of high energy/power density and long‐time cyclability. So far, desirable rich redox centers (V2+‐V5+), consolidated frameworks, and the high theoretical capacities of vanadium‐based compounds have been widely explored for practical applications. Rational materials design utilizing vanadium multiredox centers and the fundamental understanding of their charge‐transfer processes and mechanisms are critical in the development of high‐performance battery systems. The scientific importance and basic design strategies for high performance V‐based anode/cathode materials, structure‐function properties and state‐of‐the‐art understanding of V‐based electrode materials are herein classified and highlighted alongside their design strategies. The important role of the valence electron layer of vanadium, and the scientific advances of vanadium partitions in other electrochemical behaviors are also summarized in detail. Finally, relevant strategies and perspectives discussed in this review provide practical guidance to explore the undiscovered potentials of multi‐electron reaction relationships of not only V‐based composites, but also other types of electrode materials. [ABSTRACT FROM AUTHOR]

Graphite shows great potential as an anode material for rechargeable metal‐ion batteries because of its high abundance and low cost. However, the electrochemical performance of graphite anode materials for rechargeable potassium‐ion batteries needs to be further improved. Reported herein is a natural graphite with superior rate performance and cycling stability obtained through a unique K+‐solvent co‐intercalation mechanism in a 1 m KCF3SO3 diethylene glycol dimethyl ether electrolyte. The co‐intercalation mechanism was demonstrated by ex situ Fourier transform infrared spectroscopy and in situ X‐ray diffraction. Moreover, the structure of the [K‐solvent]+ complexes intercalated with the graphite and the conditions for reversible K+‐solvent co‐intercalation into graphite are proposed based on the experimental results and first‐principles calculations. This work provides important insights into the design of natural graphite for high‐performance rechargeable potassium‐ion batteries. [ABSTRACT FROM AUTHOR]

Titanium‐based polyanions have been intensively investigated for sodium‐ion batteries owing to their superior structural stability and thermal safety. However, their low working potential hindered further applications. Now, a cation and anion dual doping strategy is used to boost the redox potential of Ti‐based cathodes of Na3Ti0.5V0.5(PO3)3N as a new cathode material for sodium ion batteries. Both the Ti3+/Ti4+ and V3+/V4+ redox couples are reversibly accessed, leading to two distinctive voltage platforms at ca. 3.3 V and ca. 3.8 V, respectively. The remarkably improved cycling stability (86.3 %, 3000 cycles) can be ascribed to the near‐zero volume strain in this unusual cubic symmetry, which has been demonstrated by in situ synchrotron‐based X‐ray diffraction. First‐principles calculations reveal its well‐interconnected 3D Na diffusion pathways with low energy barriers, and the two‐sodium‐extracted intermediate NaTi0.5V0.5(PO3)3N is also a stable phase according to formation energy calculations. [ABSTRACT FROM AUTHOR]

Electrocatalysis for cathodic oxygen is of great significance for achieving high-performance lithium–oxygen batteries. Herein, we report a facile and green method to prepare an interconnected nanoporous three-dimensional (3D) architecture, which is composed of RuO2 nanogranulates coated with few layers of carbon. The as-prepared 3D nanoporous RuO2@C nanostructure can demonstrate a high initial specific discharge capacity of 4000 mA h g−1 with high round-trip efficiency of 95%. Meanwhile, the nanoporous RuO2@C could achieve stable cycling performance with a fixed capacity of 1500 mA h g−1 over 100 cycles. The terminal discharge and charge potentials of nanoporous RuO2@C are well maintained with minor potential variation of 0.14 and 0.13 V at the 100th cycle, respectively. In addition, the formation of discharge products is monitored by using in situ high-energy synchrotron X-ray diffraction (XRD). [ABSTRACT FROM AUTHOR]

Structural evolution of the cathode during cycling plays a vital role in the electrochemical performance of sodium‐ion batteries. A strategy based on engineering the crystal structure coupled with chemical substitution led to the design of the layered P2@P3 integrated spinel oxide cathode Na0.5Ni0.1Co0.15Mn0.65Mg0.1O2, which shows excellent sodium‐ion half/full battery performance. Combined analyses involving scanning transmission electron microscopy with atomic resolution as well as in situ synchrotron‐based X‐ray absorption spectra and in situ synchrotron‐based X‐ray diffraction patterns led to visualization of the inherent layered P2@P3 integrated spinel structure, charge compensation mechanism, structural evolution, and phase transition. This study provides an in‐depth understanding of the structure‐performance relationship in this structure and opens up a novel field based on manipulating structural evolution for the design of high‐performance battery cathodes. [ABSTRACT FROM AUTHOR]

With the unprecedentedly increasing demand for renewable and clean energy sources, the sodium‐ion battery (SIB) is emerging as an alternative or complementary energy storage candidate to the present commercial lithium‐ion battery due to the abundance and low cost of sodium resources. Layered transition metal oxides and Prussian blue analogs are reviewed in terms of their commercial potential as cathode materials for SIBs. The recent progress in research on their half cells and full cells for the ultimate application in SIBs are summarized. In addition, their electrochemical performance, suitability for scaling up, cost, and environmental concerns are compared in detail with a brief outlook on future prospects. It is anticipated that this review will inspire further development of layered transition metal oxides and Prussian blue analogs for SIBs, especially for their emerging commercialization. [ABSTRACT FROM AUTHOR]

Iron-based Prussian blue analogs are promising low-cost and easily prepared cathode materials for sodium-ion batteries. Their materials quality and electrochemical performance are heavily reliant on the precipitation process. Here we report a controllable precipitation method to synthesize high-performance Prussian blue for sodium-ion storage. Characterization of the nucleation and evolution processes of the highly crystalline Prussian blue microcubes reveals a rhombohedral structure that exhibits high initial Coulombic efficiency, excellent rate performance, and cycling properties. The phase transitions in the as-obtained material are investigated by synchrotron in situ powder X-ray diffraction, which shows highly reversible structural transformations between rhombohedral, cubic, and tetragonal structures upon sodium-ion (de)intercalations. Moreover, the Prussian blue material from a large-scale synthesis process shows stable cycling performance in a pouch full cell over 1000 times. We believe that this work could pave the way for the real application of Prussian blue materials in sodium-ion batteries. Here the authors deploy a scalable synthesis route to prepare sodium-rich Na2−xFeFe(CN)6 cathode materials for sodium-ion battery. The highly reversible structural evolution during cycling between rhombohedral, cubic and tetragonal phases is the key to enable the good performance. [ABSTRACT FROM AUTHOR]

Herein, we introduce a 4.0 V class high‐voltage cathode material with a newly recognized sodium superionic conductor (NASICON)‐type structure with cubic symmetry (space group P213), Na3V(PO3)3N. We synthesize an N‐doped graphene oxide‐wrapped Na3V(PO3)3N composite with a uniform carbon coating layer, which shows excellent rate performance and outstanding cycling stability. Its air/water stability and all‐climate performance were carefully investigated. A near‐zero volume change (ca. 0.40 %) was observed for the first time based on in situ synchrotron X‐ray diffraction, and the in situ X‐ray absorption spectra revealed the V3.2+/V4.2+ redox reaction with high reversibility. Its 3D sodium diffusion pathways were demonstrated with distinctive low energy barriers. Our results indicate that this high‐voltage NASICON‐type Na3V(PO3)3N composite is a competitive cathode material for sodium‐ion batteries and will receive more attention and studies in the future. [ABSTRACT FROM AUTHOR]

Emerging rechargeable sodium‐ion storage systems—sodium‐ion and room‐temperature sodium–sulfur (RT‐NaS) batteries—are gaining extensive research interest as low‐cost options for large‐scale energy‐storage applications. Owing to their abundance, easy accessibility, and unique physical and chemical properties, sulfur‐based materials, in particular metal sulfides (MSx) and elemental sulfur (S), are currently regarded as promising electrode candidates for Na‐storage technologies with high capacity and excellent redox reversibility based on multielectron conversion reactions. Here, we present current understanding of Na‐storage mechanisms of the S‐based electrode materials. Recent progress and strategies for improving electronic conductivity and tolerating volume variations of the MSx anodes in Na‐ion batteries are reviewed. In addition, current advances on S cathodes in RT‐NaS batteries are presented. We outline a novel emerging concept of integrating MSx electrocatalysts into conventional carbonaceous matrices as effective polarized S hosts in RT‐NaS batteries as well. This comprehensive progress report could provide guidance for research toward the development of S‐based materials for the future Na‐storage techniques. [ABSTRACT FROM AUTHOR]

Considering that the high capacity, long-term cycle life, and high-rate capability of anode materials for sodium-ion batteries (SIBs) is a bottleneck currently, a series of Co-doped FeS2 solid solutions with different Co contents were prepared by a facile solvothermal method, and for the first time their Na-storage properties were investigated. The optimized Co0.5Fe0.5S2 (Fe0.5) has discharge capacities of 0.220 Ah g−1 after 5000 cycles at 2 A g−1 and 0.172 Ah g−1 even at 20 A g−1 with compatible ether-based electrolyte in a voltage window of 0.8-2.9 V. The Fe0.5 sample transforms to layered Na xCo0.5Fe0.5S2 by initial activation, and the layered structure is maintained during following cycles. The redox reactions of Na xCo0.5Fe0.5S2 are dominated by pseudocapacitive behavior, leading to fast Na+ insertion/extraction and durable cycle life. A Na3V2(PO4)3/Fe0.5 full cell was assembled, delivering an initial capacity of 0.340 Ah g−1. [ABSTRACT FROM AUTHOR]

A novel and low-cost FeP anode with a high capacity of 764.7 mA h g−1 synthesized by a ball-milling method is reported for sodium ion batteries. Ex situ X-ray diffraction and transmission electron microscopy have been used to explore the sodium storage mechanism of FeP. [ABSTRACT FROM AUTHOR]

With the current rapid growth of commercial applications for flexible and wearable optoelectronic devices, flexible power sources are very much in demand. Herein, a facile strategy to grow cobalt nanoparticles encapsulated in nitrogen‐doped carbon nanotube arrays on flexible carbon fiber cloth as self‐supported electrodes for high‐performance flexible zinc–air batteries is developed. Benefiting from high electrical conductivity and multiple active sites as well as free polymer binder, the self‐supported electrode exhibits excellent electrocatalytic activity. The maximum power density of a zinc–air battery using the self‐supported electrode as air cathode is higher than that of the zinc–air battery with Pt/C+IrO2 as air electrode. Furthermore, the zinc–air battery can be stably operated under external stress without obvious loss of the electrochemical performance. This work opens up a new pathway for the rational design of flexible electrodes for high‐performance flexible power sources. [ABSTRACT FROM AUTHOR]

Recently, room‐temperature stationary sodium‐ion batteries (SIBs) have received extensive investigations for large‐scale energy storage systems (EESs) and smart grids due to the huge natural abundance and low cost of sodium. The SIBs share a similar "rocking‐chair" sodium storage mechanism with lithium‐ion batteries; thus, selecting appropriate electrodes with a low cost, satisfactory electrochemical performance, and high reliability is the key point for the development for SIBs. On the other hand, the carefully chosen elements in the electrodes also largely determine the cost of SIBs. Therefore, earth‐abundant‐metal‐based compounds are ideal candidates for reducing the cost of electrodes. Among all the high‐abundance and low‐cost metal elements, cathodes containing iron and/or manganese are the most representative ones that have attracted numerous studies up till now. Herein, recent advances on both iron‐ and manganese‐based cathodes of various types, such as polyanionic, layered oxide, MXene, and spinel, are highlighted. The structure–function property for the iron‐ and manganese‐based compounds is summarized and analyzed in detail. With the participation of iron and manganese in sodium‐based cathode materials, real applications of room‐temperature SIBs in large‐scale EESs will be greatly promoted and accelerated in the near future. State‐of‐the‐art high‐abundance and low‐cost metal‐based cathode materials for sodium‐ion batteries are comprehensively summarized and analyzed, providing a step toward the real‐life, commercial application of sodium‐ion batteries. Constructive suggestions and guidance are provided and future prospects regarding this promising field are discussed. [ABSTRACT FROM AUTHOR]

• Side reactions at the Na metal anode with oxidative contaminations are discussed. • Dendrite and dead sodium formation and suppression strategies are reviewed. • Electrostatic shield effect and robust SEI suppress dendrite formation. • Alternative Na anode mitigate side reactions and dendrite formation. Aprotic Na-O 2 batteries attract increasing attention for the low charging/discharging overpotentials, high energy density, and low cost. Significant progress has been achieved in the battery system, but challenges remain in constructing reliable Na anodes. This review presents an overview of the fundamental understanding of Na anodes in aprotic Na-O 2 batteries, including chemical reactivity of Na metal and dendrite formation mechanism. The constructing strategies are summarized as mechanical reinforcement of separators, electrolyte modifications, and electrode structure and material design. Perspectives are envisioned for the further development of durable Na anodes for aprotic Na-O 2 batteries. [ABSTRACT FROM AUTHOR]