Fe‐Based Tunnel‐Type Na0.61[Mn0.27Fe0.34Ti0.39]O2 Designed by a New Strategy as a Cathode Material for Sodium‐Ion Batteries

Sodium‐ion batteries are promising for grid‐scale storage applications due to the natural abundance and low cost of sodium. However, few electrodes that can meet the requirements for practical applications are available today due to the limited routes to exploring new materials. Here, a new strategy is proposed through partially/fully substituting the redox couple of existing negative electrodes in their reduced forms to design the corresponding new positive electrode materials. The power of this strategy is demonstrated through the successful design of new tunnel‐type positive electrode materials of Na_0.61[Mn_0.61‐xFe_xTi_0.39]O₂, composed of non‐toxic and abundant elements: Na, Mn, Fe, Ti. In particular, the designed air‐stable Na_0.61[Mn_0.27Fe_0.34Ti_0.39]O₂ shows a usable capacity of ≈90 mAh g^?1, registering the highest value among the tunnel‐type oxides, and a high storage voltage of 3.56 V, corresponding to the Fe³⁺/Fe⁴⁺ redox couple realized for the first time in non‐layered oxides, which was confirmed by X‐ray absorption spectroscopy and Mössbauer spectroscopy. This new strategy would open an exciting route to explore electrode materials for rechargeable batteries.     

Rational Construction of Self‐Standing Sulfur‐Doped Fe2O3 Anodes with Promoted Energy Storage Capability for Wearable Aqueous Rechargeable NiCo‐Fe Batteries

Aqueous rechargeable Ni‐Fe batteries featuring an ultra‐flat discharge plateau, low cost, and outstanding safety characteristics show promising prospects for application in wearable energy storage. In particular, fiber‐shaped Ni‐Fe batteries will enable textile‐based energy supply for wearable electronics. However, the development of fiber‐shaped Ni‐Fe batteries is currently challenged by the performance of fibrous Fe‐based anode materials. In this context, this study describes the fabrication of sulfur‐doped Fe₂O₃ nanowire arrays (S‐Fe₂O₃ NWAs) grown on carbon nanotube fibers (CNTFs) as an innovative anode material (S‐Fe₂O₃ NWAs/CNTF). Encouragingly, first‐principle calculations reveal that S‐doping in Fe₂O₃ can dramatically reduce the band gap from 2.34 to 1.18 eV and thus enhance electronic conductivity. The novel developed S‐Fe₂O₃ NWAs/CNTF electrode is further demonstrated to deliver a very high capacity of 0.81 mAh cm^?2 at 4 mA cm^?2. This value is almost sixfold higher than that of the pristine Fe₂O₃ NWAs/CNTF electrode. When a cathode containing zinc‐nickel‐cobalt oxide (ZNCO)@Ni(OH)₂ NWAs heterostructures is used, 0.46 mAh cm^?2 capacity and 67.32 mWh cm^?3 energy density are obtained for quasi‐solid‐state fiber‐shaped NiCo‐Fe batteries, which outperform most state‐of‐the‐art fiber‐shaped aqueous rechargeable batteries. These findings offer an innovative and feasible route to design high‐performance Fe‐based anodes and may inspire new development for the next‐generation wearable Ni‐Fe batteries.     

Superior Lithium Storage Properties of β‐FeOOH

Several crystal forms of FeOOH are recently reported to be highly promising for lithium storage due to their high capacity, low cost, and environmental friendliness. In particular, β‐FeOOH has shown a capacity of ≈1000 mAh g^?1, which is comparable to other promising iron‐based anodes, such as Fe₂O₃ and Fe₃O_4. However, its storage mechanisms are unclear and the potential for further improvement remains unexplored. Here, it is shown that this material can have a very high reversible capacity of ≈1400 mAh g^?1, which is 20%–40% higher than Fe₂O₃ and Fe₃O₄. Such a high capacity is delivered from a series of reactions including intercalation and conversion reactions, formation/deformation of solid‐state electrolyte interface layers and interfacial storage. The mechanisms are studied by a combination of electrochemical and X‐ray absorption near edge spectroscopic approaches. Moreover, very long cycling performance, that is, after even more than 3000 cycles the material still has a significant capacity of more than 800 mAh g^?1, is obtained by a simple electrode design involving introducing a rigid support into porous electrodes. Such long cycling performance is for the first time achieved for high‐capacity materials based on conversion reactions.     

Iron‐Oxide‐Based Advanced Anode Materials for Lithium‐Ion Batteries

Iron oxides, such as Fe₂O₃ and Fe₃O₄, have recently received increased attention as very promising anode materials for rechargeable lithium‐ion batteries (LIBs) because of their high theoretical capacity, non‐toxicity, low cost, and improved safety. Nanostructure engineering has been demonstrated as an effective approach to improve the electrochemical performance of electrode materials. Here, recent research progress in the rational design and synthesis of diverse iron oxide‐based nanomaterials and their lithium storage performance for LIBs, including 1D nanowires/rods, 2D nanosheets/flakes, 3D porous/hierarchical architectures, various hollow structures, and hybrid nanostructures of iron oxides and carbon (including amorphous carbon, carbon nanotubes, and graphene). By focusing on synthesis strategies for various iron‐oxide‐based nanostructures and the impacts of nanostructuring on their electrochemical performance, novel approaches to the construction of iron‐oxide‐based nanostructures are highlighted and the importance of proper structural and compositional engineering that leads to improved physical/chemical properties of iron oxides for efficient electrochemical energy storage is stressed. Iron‐oxide‐based nanomaterials stand a good chance as negative electrodes for next generation LIBs.     

A High‐Energy Density Asymmetric Supercapacitor Based on Fe2O3 Nanoneedle Arrays and NiCo2O4/Ni(OH)2 Hybrid Nanosheet Arrays Grown on SiC Nanowire Networks as Free‐Standing Advanced Electrodes

In this paper, a novel freestanding core‐branch negative and positive electrode material through integrating trim aligned Fe₂O₃ nanoneedle arrays (Fe₂O₃ NNAs) is first proposed with typical mesoporous structures and NiCo₂O₄/Ni(OH)₂ hybrid nanosheet arrays (NiCo₂O₄/Ni(OH)₂ HNAs) on SiC nanowire (SiC NW) skeletons with outstanding resistance to oxidation and corrosion, good conductivity, and large‐specific surface area. The original built SiC NWs@Fe₂O₃ NNAs is validated to be a highly capacitive negative electrode (721 F g^?1 at 2 A g^?1, i.e., 1 F cm^?2 at 2.8 mA cm^?2), matching well with the similarly constructed SiC NWs@NiCo₂O₄/Ni(OH)₂ HNAs positive electrode (2580 F g^?1 at 4 A g^?1, i.e., 3.12 F cm^?2 at 4.8 mA cm^?2). Contributed by the uniquely engineered electrodes, a high‐performance asymmetric supercapacitor (ASC) is developed, which can exhibit a maximum energy density of 103 W h kg^?1 at a power density of 3.5 kW kg^?1, even when charging the device within 6.5 s, the energy density can still maintain as high as 45 W h kg^?1 at 26.1 kW kg^?1, and the ASC manifests long cycling lifespan with 86.6% capacitance retention even after 5000 cycles. This pioneering work not only offers an attractive strategy for rational construction of high‐performance SiC NW‐based nanostructured electrodes materials, but also provides a fresh route for manufacturing next‐generation high‐energy storage and conversion systems.     

Rechargeable Iron–Sulfur Battery without Polysulfide Shuttling

Sulfur represents one of the most promising cathode materials for next‐generation batteries; however, the widely observed polysulfide dissolution/shuttling phenomenon in metal–sulfur redox chemistries has severely restricted their applications. Here it is demonstrated that when pairing the sulfur electrode with the iron metal anode, the inherent insolubility of iron sulfides renders the shuttling‐free nature of the Fe–S electrochemical reactions. Consequently, the sulfur electrode exhibits promising performance for Fe²⁺ storage, where a high capacity of ≈1050 mAh g^?1, low polarization of ≈0.16 V as well as stable cycling of 150 cycles are realized. The Fe–S redox mechanism is further revealed as an intriguing stepwise conversion of S₈ ? FeS₂ ? Fe₃S₄ ? FeS, where a low volume expansion of ≈32.6% and all‐solid‐state phase transitions facilitate the reaction reversibility. This study suggests an alternative direction to exploit sulfur electrodes in rechargeable transition metal–sulfur batteries.     

Electrochemical Activity of Hematite Phase in Full‐Cell Li‐ion Assemblies

Exploring negative electrodes for high‐performance Li‐ion power packs and related issues that are hampering their commercialization is a particularly important topic of research. This study investigates the electrochemical activity of low‐cost and typical conversion‐type hematite (α‐Fe₂O₃) anodes in practical assemblies, namely, full‐cell configurations. Numerous studies have reported improvements in the electrochemical activity of α‐Fe₂O₃ in half cells with Li by tuning the morphology or formulating composites with carbonaceous materials. However, these studies are not sufficient to market them for practical assemblies with conventional cathodes like LiCoO₂, LiMn₂O₄, LiFePO₄ and its derivatives, mainly because of large polarization problems, such as, hysteresis, irreversible capacity loss, volume variation, and capacity fading. Eliminating these issues in the fabrication of full cells is necessary, and this study reviews relevant research activities and discusses future prospects in the field.     

Partial Nitridation‐Induced Electrochemistry Enhancement of Ternary Oxide Nanosheets for Fiber Energy Storage Device

Fiber‐based power sources are receiving interest in terms of application in wearable electronic devices. Herein, fiber‐shaped all‐solid‐state asymmetric energy storage devices are fabricated based on a partially nitridized NiCo₂O₄ hybrid nanostructures on graphite fibers (GFs). The surface nitridation leads to a 3D “pearled‐veil” network structure, in which Ni–Co–N nanospheres are mounted on NiCo₂O₄ nanosheets' electrode. It is demonstrated that the hybrid materials are more potent than the pure NiCo₂O₄ in energy storage applications due to a cooperative effect between the constituents. The Ni–Co–N segments augment the pristine oxide nanosheets by enhancing both capacity and rate performance (a specific capacity of 384.75 mAh g⁻¹ at 4 A g⁻¹, and a capacity retention of 86.5% as the current is increased to 20 A g⁻¹). The whole material system has a metallic conductivity that renders high‐rate charge and discharge, and an extremely soft feature, so that it can wrap around arbitrary‐shaped holders. All‐solid‐state asymmetric device is fabricated using Ni–Co–N/NiCo₂O₄/GFs and carbon nanotubes/GFs as the electrodes. The flexible device delivers outstanding performance compared to most oxide‐based full devices. These structured hybrid materials may find applications in miniaturized foldable energy devices.     

Vanadium Oxide Nanowire–Carbon Nanotube Binder‐Free Flexible Electrodes for Supercapacitors

Vanadium pentoxide (V₂O₅) layered nanostructures are known to have very stable crystal structures and high faradaic activity. The low electronic conductivity of V₂O₅ greatly limits the application of vanadium oxide as electrode materials and requires combining with conducting materials using binders. It is well known that the organic binders can degrade the overall performance of electrode materials and need carefully controlled compositions. In this study, we develop a simple method for preparing freestanding carbon nanotube (CNT)‐V₂O₅ nanowire (VNW) composite paper electrodes without using binders. Coin cell type (CR2032) supercapacitors are assembled using the nanocomposite paper electrode as the anode and high surface area carbon fiber electrode (Spectracarb 2225) as the cathode. The supercapacitor with CNT‐VNW composite paper electrode exhibits a power density of 5.26 kW Kg^?1 and an energy density of 46.3 Wh Kg^?1. (Li)VNWs and CNT composite paper electrodes can be fabricated in similar manner and show improved overall performance with a power density of 8.32 kW Kg^?1 and an energy density of 65.9 Wh Kg^?1. The power and energy density values suggest that such flexible hybrid nanocomposite paper electrodes may be useful for high performance electrochemical supercapacitors.     

Wearable High‐Performance Supercapacitors Based on Silver‐Sputtered Textiles with FeCo2S4–NiCo2S4 Composite Nanotube‐Built Multitripod Architectures as Advanced Flexible Electrodes

To achieve high‐performance wearable supercapacitors (SCs), a new class of flexible electrodes with favorable architectures allowing large porosity, high conductivity, and good mechanical stability is strongly needed. Here, this study reports the rational design and fabrication of a novel flexible electrode with nanotube‐built multitripod architectures of ternary metal sulfides' composites (FeCo₂S₄–NiCo₂S₄) on a silver‐sputtered textile cloth. Silver sputtering is applicable to almost all kinds of textiles, and S^2? concentration is optimized during sulfidation process to achieve such architectures and also a complete sulfidation assuring high conductivity. New insights into concentration‐dependent sulfidation mechanism are proposed. The additive‐free FeCo₂S₄–NiCo₂S₄ electrode shows a high specific capacitance of 1519 F g^?1 at 5 mA cm^?2 and superior rate capability (85.1% capacitance retention at 40 mA cm^?2). All‐solid‐state SCs employing these advanced electrodes deliver high energy density of 46 W h kg^?1 at 1070 W kg^?1 as well as achieve remarkable cycling stability retaining 92% of initial capacitance after 3000 cycles at 10 mA cm^?2, and outstanding reliability with no capacitance degradation under large twisting. These are attributed to the components' synergy assuring rich redox reactions, high conductivity as well as highly porous but robust architectures. An almost linear increase in capacitance with devices' area indicates possibility to meet various energy output requirements. This work provides a general, low‐cost route to wearable power sources.     

High‐Performance Flexible Solid‐State Ni/Fe Battery Consisting of Metal Oxides Coated Carbon Cloth/Carbon Nanofiber Electrodes

Aqueous Ni/Fe batteries have great potential as flexible energy storage devices, owing to their low cost, low toxicity, high safety, and high energy density. However, the poor cycling stability has limited the widely expected application of Ni/Fe batteries, while the use of heavy metal substrates cannot meet the basic requirement for flexible devices. In this work, a flexible type of solid‐state Ni/Fe batteries with high energy and power densities is rationally developed using needle‐like Fe₃O₄ and flake‐like NiO directly grown on carbon cloth/carbon nanofiber (CC–CF) matrix as the anode and cathode, respectively. The hierarchical CC–CF substrate with high electric conductivity and good flexibility serves as an ideal support for guest active materials of nanocrystalline Fe₃O₄ and NiO, which can effectively buffer the volume change giving rise to good cycling ability. By utilizing a gel electrolyte, a robust and mechanically flexible quasi‐solid‐state Ni/Fe full cell can be assembled. It demonstrates optimal electrochemical performance, such as high energy density (5.2 mWh cm^?3 and 94.5 Wh Kg^?1), high power density (0.64 W cm^?3 and 11.8 KW Kg^?1), together with excellent cycling ability. This work provides an example of solid‐state alkaline battery with high electrochemical performance and mechanical flexibility, holding great potential for future flexible electronic devices.     

Facile Synthesis of a 3D Nanoarchitectured Li4Ti5O12 Electrode for Ultrafast Energy Storage

Despite enormous efforts devoted to the development of high‐performance batteries, the obtainable energy and power density, durability, and affordability of the existing batteries are still inadequate for many applications. Here, a self‐standing nanostructured electrode with ultrafast cycling capability is reported by in situ tailoring Li₄Ti₅O₁₂ nanocrystals into a 3D carbon current collector (derived from filter paper) through a facile wet chemical process involving adsorption of titanium source, boiling treatment, and subsequent chemical lithiation. This 3D architectural electrode is charged/discharged to ≈60% of the theoretical capacity of Li₄Ti₅O₁₂ in ≈21 s at 100 C rate (17 500 mA g^?1 ), which also shows stable cycling performance for 1000 cycles at a cycling rate of 50 C. Additionally, modified 3D carbon current collector with much smaller pores and finer fiber diameters are further used, which significantly improve the specific capacity based on the weight of the entire electrode. These novel electrodes are promising for high‐power applications such as electric vehicles and smart grids. This unique electrode architecture also simplifies the electrode fabrication process and significantly enhances current collection efficiency (especially at high rate). Further, the conceptual electrode design is applicable to other oxide electrode materials for high‐performance batteries, fuel cells, and supercapacitors.     

Achieving Ultrahigh Energy Densities of Supercapacitors with Porous Titanium Carbide/Boron‐Doped Diamond Composite Electrodes

The energy densities of most supercapacitors (SCs) are low, hindering their practical applications. To construct SCs with ultrahigh energy densities, a porous titanium carbide (TiC)/boron‐doped diamond (BDD) composite electrode is synthesized on a titanium plate that is pretreated using a plasma electrolytic oxidation (PEO) technique. The porous and nanometer‐thick TiO₂ layer formed during PEO process prevents the formation of brittle titanium hydride and enhances the BDD growth during chemical vapor deposition processes. Meanwhile, the in situ conversion of TiO₂ into TiC is achieved. Combination of this capacitor electrode with soluble redox electrolytes leads to the fabrication of high‐performance SCs in both aqueous and organic solutions. In 0.05 m Fe(CN)₆^3?/4? + 1 m Na₂SO₄ aqueous solution, the capacitance is as high as 46.3 mF cm^?2 at a current density of 1 mA cm^?2; this capacitance remains 92% of its initial value even after 10 000 charge/discharge cycles; the energy density is up to 47.4 Wh kg^?1 at a power density of 2236 W kg^?1. The performance of constructed SCs is superior to most available SCs and some electrochemical energy storage devices like batteries. Such a porous capacitor electrode is thus promising for the construction of high‐performance SCs for practical applications.     

Confined Fe2VO4⊂Nitrogen‐Doped Carbon Nanowires with Internal Void Space for High‐Rate and Ultrastable Potassium‐Ion Storage

Developing low‐cost, high‐capacity, high‐rate, and robust earth‐abundant electrode materials for energy storage is critical for the practical and scalable application of advanced battery technologies. Herein, the first example of synthesizing 1D peapod‐like bimetallic Fe₂VO₄ nanorods confined in N‐doped carbon porous nanowires with internal void space (Fe₂VO₄?NC nanopeapods) as a high‐capacity and stable anode material for potassium‐ion batteries (KIBs) is reported. The peapod‐like Fe₂VO₄?NC nanopeapod heterostructures with interior void space and external carbon shell efficiently prevent the aggregation of the active materials, facilitate fast transportation of electrons and ions, and accommodate volume variation during the cycling process, which substantially boosts the rate and cycling performance of Fe₂VO₄. The Fe₂VO₄?NC electrode exhibits high reversible specific depotassiation capacity of 380 mAh g^?1 at 100 mA g^?1 after 60 cycles and remarkable rate capability as well as long cycling stability with a high capacity of 196 mAh g^?1 at 4 A g^?1 after 2300 cycles. The first‐principles calculations reveal that Fe₂VO₄?NC nanopeapods have high ionic/electronic conductivity characteristics and low diffusion barriers for K⁺‐intercalation. This study opens up new way for investigating high‐capacity metal oxide as high‐rate and robust electrode materials for KIBs.     

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li‐ and Mn‐Rich Cathode Materials for Li‐Ion Batteries

Li and Mn‐rich layered oxides, xLi₂MnO₃·(1–x)LiMO₂ (M=Ni, Mn, Co), are promising cathode materials for Li‐ion batteries because of their high specific capacity that can exceed 250 mA h g^?1. However, these materials suffer from high 1^st cycle irreversible capacity, gradual capacity fading, low rate capability, a substantial charge‐discharge voltage hysteresis, and a large average discharge voltage decay during cycling. The latter detrimental phenomenon is ascribed to irreversible structural transformations upon cycling of these cathodes related to potentials ≥4.5 V required for their charging. Transition metal inactivation along with impedance increase and partial layered‐to‐spinel transformation during cycling are possible reasons for the detrimental voltage fade. Doping of Li, Mn‐rich materials by Na, Mg, Al, Fe, Co, Ru, etc. is useful for stabilizing capacity and mitigating the discharge‐voltage decay of xLi₂MnO₃·(1–x)LiMO₂ electrodes. Surface modifications by thin coatings of Al₂O₃, V₂O₅, AlF₃, AlPO₄, etc. or by gas treatment (for instance, by NH₃) can also enhance voltage and capacity stability during cycling. This paper describes the recent literature results and ongoing efforts from our groups to improve the performance of Li, Mn‐rich materials. Focus is also on preparation of cobalt‐free cathodes, which are integrated layered‐spinel materials with high reversible capacity and stable performance.     

Exceptionally Enhanced Electrode Activity of (Pr,Ce)O2−δ‐Based Cathodes for Thin‐Film Solid Oxide Fuel Cells

It is shown that an electrochemically‐driven oxide overcoating substantially improves the performance of metal electrodes in high‐temperature electrochemical applications. As a case study, Pt thin films are overcoated with (Pr,Ce)O_2?δ (PCO) by means of a cathodic electrochemical deposition process that produces nanostructured oxide layers with a high specific surface area and uniform metal coverage and then the coated films are examined as an O₂‐electrode for thin‐film‐based solid oxide fuel cells. The combination of excellent conductivity, reactivity, and durability of PCO dramatically improves the oxygen reduction reaction rate while maintaining the nanoscale architecture of PCO layers and thus the performance of the PCO‐coated Pt thin‐film electrodes at high temperatures. As a result, with an oxide coating step lasting only 5 min, the electrode resistance is successfully reduced by more than 1000 times at 500 °C in air. These observations provide a new direction for the design of high‐performance electrodes for high‐temperature electrochemical cells.     

Research Progress on Negative Electrodes for Practical Li‐Ion Batteries: Beyond Carbonaceous Anodes

Research activities related to the development of negative electrodes for construction of high‐performance Li‐ion batteries (LIBs) with conventional cathodes such as LiCoO₂, LiFePO₄, and LiMn₂O₄ are described. The anode materials are classified in to three main categories, insertion, conversion, and alloying type, based on their reactivity with Li. Although numerous materials have been proposed (i.e., for half‐cell assembly), few of them have reached commercial applications, apart from graphite, Li₄Ti₅O₁₂, Si, and Sn‐Co‐C. This clearly demonstrates that full‐cell studies are desperately needed rather than just characterizing materials in half‐cell assemblies. Additionally, the performance of such anodes in practical Li‐ion configurations (full‐cell) is much more important than merely proposing materials for LIBs. Irreversible capacity loss, huge volume variation, unstable solid electrolyte interface layer formation, and poor cycleability are the main issues for conversion and alloy type anodes. This review addresses how best to circumvent the mentioned issues during the construction of Li‐ion cells and the future prospects of such anodes are described in detail.     

Micro‐ and Nano‐Structured Vanadium Pentoxide (V2O5) for Electrodes of Lithium‐Ion Batteries

Vanadium pentoxide (V₂O₅) has played important roles in lithium‐ion batteries due to its unique crystalline structure. To assist researchers understanding the roles this material plays, a comprehensive and critical review is conducted based on about 250 publications. Here, we report basics and applications of micro‐ and nano‐materials of V₂O₅ and V₂O₅‐based composites. The comparative and statistical analysis leads to the discovery of several interesting phenomena. The V₂O₅ electrodes with two lithium ions have a favorable capacity performance with reversible phase formation. The excellent capacity retention is displayed in the V₂O₅ electrodes with one lithium ion inserted. In the case of three lithium ions insertion, it was found that the irreversible formation of the phase ω in Li_xV₂O₅ leads to its control. In addition, effects of additives on electrode performance, circuitry models of performance, as well as reaction routes are studied. Two unprecedented concepts of the “high capacity band” and “empirical total capacity retention” are proposed though the comprehensive statistical analysis of the reviewed data. This review provides a comprehensive collection of information of state‐of‐the‐art and recent advancement in V₂O₅ and V₂O₅‐based composite materials for electrodes. Researchers could use the information to design and develop advanced electrodes for future batteries.     

Insights into Ionic Transport and Structural Changes in Magnetite during Multiple‐Electron Transfer Reactions

Metal oxides, such as Fe₃O₄, hold promise for future battery applications due to their abundance, low cost, and opportunity for high lithium storage capacity. In order to better understand the mechanisms of multiple‐electron transfer reactions leading to high capacity in Fe₃O₄, a comprehensive investigation on local ionic transport and ordering is made by probing site occupancies of anions (O^2?) and cations (Li⁺, Fe³⁺/Fe²⁺) using multiple synchrotron X‐ray and electron‐beam techniques, in combination with ab‐initio calculations. Results from this study provide the first experimental evidence that the cubic‐close‐packed (ccp) O‐anion array in Fe₃O₄ is sustained throughout the lithiation and delithiation processes, thereby enabling multiple lithium intercalation and conversion reactions. Cation displacement/reordering occurs within the ccp O‐anion framework, which leads to a series of phase transformations, starting from the inverse spinel phase and turning into intermediate rock‐salt‐like phases (Li_xFe₃O₄; 0 < x < 2), then into a cation‐segregated phase (Li₂O?FeO), and finally converting into metallic Fe and Li₂O. Subsequent delithiation and lithiation processes involve interconversion between metallic Fe and FeO‐like phases. These results may offer new insights into the structure‐determined ionic transport and electrochemical reactions in metal oxides, and those of other compounds sharing a ccp anion framework, reminiscent of magnetite.     

High‐Voltage Oxygen‐Redox‐Based Cathode for Rechargeable Sodium‐Ion Batteries

Recently, anionic‐redox‐based materials have shown promising electrochemical performance as cathode materials for sodium‐ion batteries. However, one of the limiting factors in the development of oxygen‐redox‐based electrodes is their low operating voltage. In this study, the operating voltage of oxygen‐redox‐based electrodes is raised by incorporating nickel into P2‐type Na_2/3[Zn_0.3Mn_0.7]O₂ in such a way that the zinc is partially substituted by nickel. As designed, the resulting P2‐type Na_2/3[(Ni_0.5Zn_0.5)_0.3Mn_0.7]O₂ electrode exhibits an average operating voltage of 3.5 V and retains 95% of its initial capacity after 200 cycles in the voltage range of 2.3–4.6 V at 0.1C (26 mA g^?1). Operando X‐ray diffraction analysis reveals the reversible phase transition: P2 to OP4 phase on charge and recovery to the P2 phase on discharge. Moreover, ex situ X‐ray absorption near edge structure and X‐ray photoelectron spectroscopy studies reveal that the capacity is generated by the combination of Ni²⁺/Ni⁴⁺ and O^2?/O^1? redox pairs, which is supported by first‐principles calculations. It is thought that this kind of high voltage redox species combined with oxygen redox could be an interesting approach to further increase energy density of cathode materials for not only sodium‐based rechargeable batteries, but other alkali‐ion battery systems.