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Developing high-power battery chemistry is an urgent task to buffer fluctuating renewable energies and achieve a sustainable and flexible power supply. Owing to the small size of the proton and its ultrahigh mobility in water via the Grotthuss mechanism, aqueous proton batteries are an attractive candidate for high-power energy storage devices. Grotthuss proton transfer is ultrafast owing to the hydrogen-bonded networks of water molecules. In this work, similar continuous hydrogen bond networks in a dense oxide-ion array of solid α-MoO3 are discovered, which facilitate the anhydrous proton transport even without structural water. The fast proton transfer and accumulation that occurs during (de)intercalation in α-MoO3 is unveiled using both experiments and first-principles calculations. Coupled with a zinc anode and a superconcentrated Zn2+ /H+ electrolyte, the proton-transport mechanism in anhydrous hydrogen-bonded networks realizes an aqueous MoO3 -Zn battery with large capacity, long life, and fast charge-discharge abilities.
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We report Na2Fe(HPO3)2 as the first HPO32--based iron(ii) cathode material for sodium-ion batteries, which delivers a reversible capacity of approximately 100 mA h g-1 at an average reaction voltage of 3.1 V. In situ X-ray diffraction and ex situ57Fe Mössbauer spectroscopy clarify reversible (de)sodiation associated with the Fe3+/Fe2+ redox reaction.
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The development of high-voltage cathode materials composed of abundant metals for rechargeable batteries is a crucial task to realize higher energy density in large-scale electrical energy storage systems. Here we report a reversible Cr4+/Cr3+ redox reaction at 4.5 V vs. Na/Na+ in NASICON-type Na2CrTi(PO4)3 (NCTP). An unstable Cr4+/Cr3+ redox in Na3Cr2(PO4)3 is successfully stabilized by the substitution of Ti with Cr. The charge/discharge mechanism of NCTP was studied by powder X-ray diffraction and soft X-ray absorption spectroscopy.
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Lithium- and sodium-rich layered transition-metal oxides have recently been attracting significant interest because of their large capacity achieved by additional oxygen-redox reactions. However, layered transition-metal oxides exhibit structural degradation such as cation migration, layer exfoliation or cracks upon deep charge, which is a major obstacle to achieve higher energy-density batteries. Here we demonstrate a self-repairing phenomenon of stacking faults upon desodiation from an oxygen-redox layered oxide Na2RuO3, realizing much better reversibility of the electrode reaction. The phase transformations upon charging A2MO3 (A: alkali metal) can be dominated by three-dimensional Coulombic attractive interactions driven by the existence of ordered alkali-metal vacancies, leading to counterintuitive self-repairing of stacking faults and progressive ordering upon charging. The cooperatively ordered vacancy in lithium-/sodium-rich layered transition-metal oxides is shown to play an essential role, not only in generating the electro-active nonbonding 2p orbital of neighbouring oxygen but also in stabilizing the phase transformation for highly reversible oxygen-redox reactions.
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Owing to developments in theoretical chemistry and computer power, the combination of calculations and experiments is now standard practice in understanding and developing new materials for battery systems. Here, we briefly review our recent combined studies based on density functional theory and molecular dynamics calculations for electrode and electrolyte materials for sodium-ion batteries. These findings represent case studies of successful combinations of experimental and theoretical methods.
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Na2 FePO4 F is a promising cathode material for a Na-ion battery because of its high electronic capacity and good cycle performance. In this work, first principle calculations combined with cluster expansion and the Monte Carlo method have been applied to analyze the charge and discharge processes of Na2 FePO4 F by examining the voltage curve and the phase diagram. As a result of the density functional theory calculation and experimental verification with structural analysis, we found that the most stable structure of Na1.5 FePO4 F has the P21 /b11 space group, which has not been reported to date. The estimated voltage curve has two clear plateaus caused by the two-phase structure composed of P21 /b11 Na1.5 FePO4 F and Pbcn Na2 FePO4 F or Na1 FePO4 F and separated along the c-axis direction. The phase diagram shows the stability of the phase-separated structure. Considering that Na2 FePO4 F has diffusion paths in the a- and c-axis directions, Na2 FePO4 F has both innerphase and interphase diffusion paths. We suggest that the stable two-phase structure and the diffusion paths to both the innerphase and interphases are a key for the very clear plateau. We challenge to simulate a nonequilibrium state at high rate discharge with high temperature by introducing a coordinate-dependent chemical potential. The simulation shows agreement with the experimental discharge curve on the disappearance of the two plateaus. © 2018 Wiley Periodicals, Inc.
RESUMEN
Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na(1/3)Ru(2/3)]O2 slabs delivers a capacity of 180 mAh g(-1) (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g(-1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.
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LiFePO4 is an important cathode material for lithium-ion batteries. Regardless of the biphasic reaction between the insulating end members, Lix FePO4 , x≈0 and x≈1, optimization of the nanostructured architecture has substantially improved the power density of positive LiFePO4 electrode. The charge transport that occurs in the interphase region across the biphasic boundary is the primary stage of solid-state electrochemical reactions in which the Li concentrations and the valence state of Fe deviate significantly from the equilibrium end members. Complex interactions among Li ions and charges at the Fe sites have made understanding stability and transport properties of the intermediate domains difficult. Long-range ordering at metastable intermediate eutectic composition of Li2/3 FePO4 has now been discovered and its superstructure determined, which reflected predominant polaron crystallization at the Fe sites followed by Li(+) redistribution to optimize the Li-Fe interactions.
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Discovery of a new class of ion intercalation compounds is highly desirable due to its relevance to various electrochemical devices, such as batteries. Herein, we present a new iron-oxalato open framework, which showed reversible Na(+) intercalation/extraction. The hydrothermally synthesized K4Na2[Fe(C2O4)2]3â 2 H2O possesses one-dimensional open channels in the oxalato-bridged network, providing ion accessibility up to two Na(+) per the formula unit. The detailed studies on the structural and electronic states revealed that the framework exhibited a solid solution state almost entirely during Na(+) intercalation/extraction associated with the reversible redox of Fe. The present work demonstrates possibilities of the oxalato frameworks as tunable and robust ion intercalation electrode materials for various device applications.
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Rechargeable lithium batteries have ushered the wireless revolution over last two decades and are now matured to enable green automobiles. However, the growing concern on scarcity and large-scale applications of lithium resources have steered effort to realize sustainable sodium-ion batteries, Na and Fe being abundant and low-cost charge carrier and redox centre, respectively. However, their performance is limited owing to low operating voltage and sluggish kinetics. Here we report a hitherto-unknown material with entirely new composition and structure with the first alluaudite-type sulphate framework, Na2Fe2(SO4)3, registering the highest-ever Fe(3+)/Fe(2+) redox potential at 3.8 V (versus Na, and hence 4.1 V versus Li) along with fast rate kinetics. Rare-metal-free Na-ion rechargeable battery system compatible with the present Li-ion battery is now in realistic scope without sacrificing high energy density and high power, and paves way for discovery of new earth-abundant sustainable cathodes for large-scale batteries.
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The particle-size effects on the thermodynamic properties and kinetic behavior of a Li(x)FePO(4) electrode have a direct influence on the electrode properties. Thus, the development of high-performance Li-ion batteries containing a Li(x)FePO(4) cathode requires a complete understanding of the reaction mechanism at the atomic/nano/meso scale. In this work, we report electrochemical calorimetric and potentiometric studies on Li(x)FePO(4) electrodes with different particle sizes and clarify the particle-size effect on the reaction mechanism based on the entropy change of (de)lithiation. Electrochemical calorimetry results show that a reduction in particle size shrinks the miscibility gap of Li(x)FePO(4) while potentiometric measurements demonstrate that the Li(x)FePO(4) particles equilibrate into either a kinetically metastable state or a thermodynamically stable state depending on the particle size.
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Phase separation and transformation induced by electrochemical ion insertion are key processes in achieving efficient energy storage. Exploration of novel insertion electrode materials/reactions is particularly important to unravel the atomic/molecular-level mechanism and improve the electrochemical properties. Here, we report the unconventional phase separation of a cyanide-bridged coordination polymer, Eu[Fe(CN)6]·4H2O, under electrochemical Na-ion insertion. Detailed structural analyses performed during the electrochemical reaction revealed that, in contrast to conventional electrochemical phase separation induced by the elastic interaction between nearest neighbors, the phase separation of NaxEu[Fe(CN)6]·4H2O is due to a long-range interaction, namely, cooperative rotation ordering of hexacyanoferrates. Kolmogorov-Johnson-Mehl-Avrami analysis showed that the activation energy for the phase boundary migration in NaxEu[Fe(CN)6]·4H2O is lower than that in other conventional electrode materials such as Li(1-x)FePO4.
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A new polymorph of lithium manganese pyrophosphate was synthesized by low-temperature solid-state synthesis, and the crystal structure was determined. The new phase has a new type of three-dimensional framework structure, which is completely different from that found in the previous study by Adam et al., J. Solid State Chem., 2008, 181, 3110. Electrochemical measurement with a Li cell demonstrated a reversible electrochemical activity at around 4 V.
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Coordination polymers have significant potential for new functionality paradigms due to the intrinsic tunability of both their electronic and structural properties. In particular, octacyanometallate-bridged coordination polymers have the extended structural and magnetic diversity to achieve novel functionalities. We demonstrate that [Mn(H2O)][Mn(HCOO)(2/3)(H2O)(2/3)](3/4)[Mo(CN)8]·H2O can exhibit electrochemical alkali-ion insertion/extraction with high durability. The high durability is explained by the small lattice change of less than 1% during the reaction, as evidenced by ex situ X-ray diffraction analysis. The ex situ X-ray absorption spectroscopy revealed reversible redox of the octacyanometallate. Furthermore, the solid state redox of the paramagnetic [Mo(V)(CN)8](3-)/diamagnetic[Mo(IV)(CN)8](4-) couple realizes magnetic switching.
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We report the incidence of lacrimal passage impairment and specific features of corneal epitheliopathy as adverse effects of the oral anticancer drug S-1, and examine the relationship between the two pathologies. We conducted a retrospective chart review of 84 patients prescribed the anticancer drug S-1. The incidence of lacrimal passage impairment and corneal epitheliopathy was 8% and 6%, respectively. Three patients experienced both pathologies, demonstrating a moderate probability of both occurring in the same patient (kappa coefficient = 0.46). The findings show that lacrimal passage impairment and specific features of corneal epitheliopathy are likely to occur in the same individual as adverse effects of S-1.
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Ion-transport paths: combined modeling and neutron diffraction studies provide atomic-scale insights into Li(2)FeP(2)O(7), a material proposed for a new lithium-battery cathode with reversible electrode operation at the highest voltage of all known Fe-based phosphates. The results indicate that Li(+) ions are transported rapidly through a 2D network along the paths shown in green in the picture.
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We have investigated polymorphs of LiFeSO4F, tavorite and triplite, which have been reported as cathode materials for lithium ion batteries. The predicted voltages are 3.64 and 3.90 V for tavorite and triplite, respectively, which agreed excellently with experimental data. It is found that the lithiated states (LiFeSO4F) of the polymorphs are almost degenerate in energy. The difference in voltage is mainly due to the difference in the stabilities of the delithiated states (FeSO4F). This is rationalized by the Fe(3+)-Fe(3+) repulsion in the edge sharing geometry of the triplite structure.
RESUMEN
A new pyrophosphate compound Li(2)FeP(2)O(7) was synthesized by a conventional solid-state reaction, and its crystal structure was determined. Its reversible electrode operation at ca. 3.5 V vs Li was identified with the capacity of a one-electron theoretical value of 110 mAh g(-1) even for ca. 1 µm particles without any special efforts such as nanosizing or carbon coating. Li(2)FeP(2)O(7) and its derivatives should provide a new platform for related lithium battery electrode research and could be potential competitors to commercial olivine LiFePO(4), which has been recognized as the most promising positive cathode for a lithium-ion battery system for large-scale applications, such as plug-in hybrid electric vehicles.
