General Synthesis of Composition-Tunable High-Entropy Amorphous Oxides Toward High Efficiency Oxygen Evolution Reaction.

High-entropy materials have attracted much attention in the electrocatalysis field due to their unique structure, high chemical activity, and compositional tunability. However, the harsh and complex synthetic methods limit the application of such materials. Herein, a universal non-equilibrium liquid-phase synthesis strategy is reported to prepare high-entropy amorphous oxide nanoparticles (HEAO-NPs), and the composition of HEAO-NPs can be precisely controlled from tri- to ten-component. The non-equilibrium synthesis environment provided by an excessively strong reducing agent overcomes the difference in the reduction potentials of various metal ions, resulting in the formation of HEAO-NPs with a nearly equimolar ratio. The oxygen evolution reaction (OER) performance of HEAO-NPs is further improved by adjusting the composition and optimizing the electronic structure. The Fe16 Co32 Ni32 Mn10 Cu10 BOy exhibits a smaller overpotential (only 259 mV at 10 mA cm-2 ) and higher stability in OER compared with commercial RuO2 . The amorphous high-entropy structure with an optimized concentration of iron makes the binding energy of CoNi shift to a higher direction, promotes the generation of high-valence active intermediates, and accelerates the OER kinetic process. The HEAO-NPs have promising application potential in the field of catalysis, biology, and energy storage, and this work provides a general synthesis method for composition-controllable high-entropy materials.

Spontaneous redox reaction-mediated interfacial charge transfer in titanium dioxide/graphene oxide nanoanodes for rapid and durable lithium storage.

Titanium dioxide (TiO2) anodes show significant advantages in ion storage owing to their low cost, abundant sources, and small volume change during cycling. However, their intrinsic low electronic conductivity and sluggish ion diffusion coefficient restrict the application of TiO2 anodes, especially at high current densities. The construction of a covalently-bonded interface in TiO2-based composite anodes is an effective approach to solve these issues. Covalent bonds are usually formed in situ during materials synthesis processes, such as high-energy ball milling, solvothermal reactions, plasma-assisted thermal treatment, and addition of a linking agent for covalent coupling. In this study, we demonstrate that a spontaneous redox reaction between defective TiO2 powder and an oxidative graphene oxide (GO) substate can be used to form interfacial covalent bonds in composites. Different structural characterization techniques confirmed the formation of interfacial covalent bonds. Electrochemical measurements on an optimized sample showed that a specific capacity of 281.3 mA h g-1 after 200 cycles can be achieved at a current density of 1 C (1 C = 168 mA g-1). Even at a high rate of 50 C, the electrode maintained a reversible capacity of 97.0 mA h g-1. The good lithium storage performance of the electrode is a result of the uniquely designed composite electrodes with strong interfacial chemical bonds.

Enhancing potassium ions adsorption on mesoporous carbon spheres with abundant internal surface via engineering sulfur doping sites towards superior rate capability.

Mesoporous carbon spheres (MCSs) show great potential for using as high-performance anodes in potassium-ion batteries (PIBs). Design and synthesis of MCSs with suitable multiscale structures and heteroatom doping or co-doping in MCSs are successfully employed to optimize the ion and electron transportation, however, it is still a challenge to explore MCS-based anodes with satisfactory potassium storage performance. In this work, we report novel S-doped MCS samples with abundant internal surfaces for potassium storage. The S doping sites are controlled during the synthesis, and the effect of different doping sites on the potassium storage is systematically studied. It is found that S doping between the carbon layers enlarges interlayer spacing and facilitates potassium ion adsorption. Consequently, the optimized sample shows an excellent rate capability of 144 mAh/g at 5.0 A/g, and a high reversible specific capacity of 325 mAh/g after 100 cycles at 0.1 A/g with a capacity retention of 91.2%. The important role of element doping sites on ion adsorption and ion storage performance is confirmed by theoretical investigations. Controlling the doping sites in MCSs provides a new approach to designing high-performance electrodes for energy storage and conversion applications.

Microwave solvothermal synthesis of Component-Tunable High-Entropy oxides as High-Efficient and stable electrocatalysts for oxygen evolution reaction.

Transition-metal-based high-entropy oxides (HEOs) are appealing electrocatalysts for oxygen evolution reaction (OER) due to their unique structure, variable composition and electronic structure, outstanding electrocatalytic activity and stability. Herein, we propose a scalable high-efficiency microwave solvothermal strategy to fabricate HEO nano-catalysts with five earth-abundant metal elements (Fe, Co, Ni, Cr, and Mn) and tailor the component ratio to enhance the catalytic performance. (FeCoNi2CrMn)3O4 with a double Ni content exhibits the best electrocatalytic performance for OER, namely low overpotential (260 mV@10 mA cm-2), small Tafel slope and superb long-term durability without obvious potential change after 95 h in 1 M KOH. The extraordinary performance of (FeCoNi2CrMn)3O4 can be attributed to the large active surface area profiting from the nano structure, the optimized surface electronic state with high conductivity and suitable adsorption to intermediate benefitting from ingenious multiple-element synergistic effects, and the inherent structural stability of the high-entropy system. In addition, the obvious pH value dependable character and TMA+ inhibition phenomenon reveal that the lattice oxygen mediated mechanism (LOM) work together with adsorbate evolution mechanism (AEM) in the catalytic process of OER with the HEO catalyst. This strategy provides a new approach for the rapid synthesis of high-entropy oxide and inspires more rational designs of high-efficient electrocatalysts.

Enhanced Interfacial Magnetization is Responsible for the Negative Capacity Fading of Cobalt Ditelluride Anodes for Lithium Storage.

In lithium-ion batteries (LIBs), the stabilized capacities of transition metal compound anodes usually exhibit higher values than their theoretical values due to the interfacial charge storage, the formation of reversible electrolyte-derived surface layer, or interfacial magnetization. But the effectively utilizing the mechanisms to achieve novel anodes is rarely explored. Herein, a novel nanosized cobalt ditelluride (CoTe2 ) anodes with ultra-high capacity and long term stability is reported. Electrochemical tests show that the lithium storage capacity of the best sample reaches 1194.7 mA h g-1 after 150 cycles at 0.12 A g-1 , which increases by 57.8% compared to that after 20 cycles. In addition, the sample offers capacities of 546.6 and 492.1 mA h g-1 at 0.6 and 1.8 A g-1 , respectively. During cycles, CoTe2 particles (average size 20 nm) are gradually pulverized into the smaller nanoparticles (<3 nm), making the magnetization more fully due to the larger contact area of Co/Li2 Te interface, yielding an increased capacity. The negative capacity fading is observed, and verified by ex situ structural characterizations and in situ electrochemical measurements. The proposed strategy can be further extended to obtain other high-performance ferromagnetic metal based electrodes for energy storage applications.

Recent advances in in situ and operando characterization techniques for Li7La3Zr2O12-based solid-state lithium batteries.

Li7La3Zr2O12 (LLZO)-based solid-state Li batteries (SSLBs) have emerged as one of the most promising energy storage systems due to the potential advantages of solid-state electrolytes (SSEs), such as ionic conductivity, mechanical strength, chemical stability and electrochemical stability. However, there remain several scientific and technical obstacles that need to be tackled before they can be commercialised. The main issues include the degradation and deterioration of SSEs and electrode materials, ambiguity in the Li+ migration routes in SSEs, and interface compatibility between SSEs and electrodes during the charging and discharging processes. Using conventional ex situ characterization techniques to unravel the reasons that lead to these adverse results often requires disassembly of the battery after operation. The sample may be contaminated during the disassembly process, resulting in changes in the material properties within the battery. In contrast, in situ/operando characterization techniques can capture dynamic information during cycling, enabling real-time monitoring of batteries. Therefore, in this review, we briefly illustrate the key challenges currently faced by LLZO-based SSLBs, review recent efforts to study LLZO-based SSLBs using various in situ/operando microscopy and spectroscopy techniques, and elaborate on the capabilities and limitations of these in situ/operando techniques. This review paper not only presents the current challenges but also outlines future developmental prospects for the practical implementation of LLZO-based SSLBs. By identifying and addressing the remaining challenges, this review aims to enhance the comprehensive understanding of LLZO-based SSLBs. Additionally, in situ/operando characterization techniques are highlighted as a promising avenue for future research. The findings presented here can serve as a reference for battery research and provide valuable insights for the development of different types of solid-state batteries.

Graphite-like structured conductive polymer anodes for high-capacity lithium storage with optimized voltage platform.

Graphite is a widely used anode material in commercial lithium-ion batteries (LIBs), but its low theoretical specific capacity and extremely low redox potential limit its application in high-performance lithium-ion batteries. However, developing lithium-ion battery anode with high specific capacity and suitable working potential is still challenging. At present, conductive polymers with excellent properties and graphite-like structures are widely used in the field of electrochemistry, but their Li+ storage mechanism and kinetics are still unclear and need to be further investigated. Therefore, we synthesized the conducting polymer Fe3(2, 3, 6, 7, 10, 11-hexahydroxytriphenylene)2 (Fe-CAT) by the liquid phase method, in which the d-π conjugated structure and pores facilitate electron transfer and electrolyte infiltration, improving the comprehensive electrochemical performance. The Fe-CAT electrode displays a high capacity of 950 mA h g-1 at 200 mA g-1. At the current density of 5.0 A g-1, the electrode shows a reversible capacity of 322 mA h g-1 after 1000 cycles. The average lithiation voltage plateau is âˆ¼ 0.79 V. The combination of ex-situ characterization techniques and electrochemical kinetic analysis reveals the source of the excellent electrochemical performance of Fe-CAT. During the charging/discharging process, the aromatic ring in the organic ligand is involved in the redox reaction. Such results will provide new insights for the design of next-generation high-performance electrode materials for LIBs.

Highly efficient oxygen evolution reaction enabled by phosphorus-boron facilitating surface reconstruction of amorphous high-entropy materials.

Efficient, cost-effective and durable electrocatalysts are highly required to overcome the slow kinetics and high overpotential of oxygen evolution reaction (OER). Here we report a series of novel amorphous high-entropy borophosphate catalysts FeCoNiMBPOx (M = Mg, Al, Cr, Mn) prepared by a low-temperature reduction method. The leaching of boron and phosphorus accelerates the surface self-reconstruction of FeCoNiMnBPOx, and the subsequently formed high-oxidation-state metal-OOH species is beneficial to improve the catalyst performance. Moreover, the unique amorphous structure with abundant defects provides more active sites for OER. As a return, all the samples exhibit excellent OER activity and stability. Among them, FeCoNiMnBPOx with the highest conductivity and the largest electrochemical active surface area (ECSA) exhibits the best electrocatalytic performance, requiring only low overpotentials of 248 mV and 294 mV to reach current densities of 10 mA cm-2 and 100 mA cm-2, respectively. This sample also shows an exceptional durability for 50 h without a significant increase in potential, which is superior to that of the benchmark RuO2 electrocatalyst. The combination of the adsorbate evolution mechanism (AEM) and the lattice oxygen-mediated mechanism (LOM) are responsible for the excellent catalyst performance. This work provides new ideas for designing high-activity multiple-element catalysts.

In-situ synthesis of niobium-doped TiO2 nanosheet arrays on double transition metal MXene (TiNbCTx) as stable anode material for lithium-ion batteries.

Two-dimensional layered MXene material with high conductivity and good mechanical flexibility has gained wide attention in the field of energy storage. However, the practical application of MXene was hampered by its limited specific capacity and the unstable structure. Herein, a composite of in-situ grown niobium-doped TiO2 nanosheet arrays on a double transition metal MXene TiNbCTx (TiNbC@NTO) was successfully obtained via a hydrothermal pretreatment followed by in-situ partial oxidation strategy. The prepared TiNbC@NTO combines multiple advantages of both MXene and oxide, including high conductivity derived from the unoxidized MXene TiNbCTx, superior structure stability from the in-situ produced oxide between the MXene layers, which prevents structural collapse and restacking during charging and discharging, and the large layer space which promotes lithium-ion transport. The degree of oxidation of MXene can be adjusted by controlling the reaction temperature, and the oxide nonosheet turn dense with the increase of the temperature. All the oxidized MXenes show improved electrochemical performance compared with the pure TiNbCTx, and the TiNbC@NTO-500 with the appropriate degree of oxidation exhibits the highest reversible capacity, best cycling stability of 261 mAh g-1 after 500 cycles at 1.0 A g-1 among all the as-prepared composites. Furthermore, an extraordinary rate performance (148.5 mAh g-1 at 2 A g-1) was obtained based on the pseudocapacitance dominated mechanism. This work provides a new insight into improving the performance of MXene-based anode material for lithium-ion batteries.

Amorphous High-entropy Non-precious metal oxides with surface reconstruction toward highly efficient and durable catalyst for oxygen evolution reaction.

High-entropy materials (HEMs) have attracted extensive interests in exploring multicomponent systems for highly efficient and durable catalysts. Tuning composition and configuration of HEMs provides untapped opportunities for accessing better catalytic performance. Herein, we report three amorphous high-entropy transition metal oxides catalysts with uniform composition through a simple and controllable liquid phase non-equilibrium reduction method. The self-made catalyst FeCoNiMnBOx exhibits excellent oxygen evolution performance, including a low overpotential (266 mV at 10 mA cm-2), small Tafel slope (64.5 mV dec-1) and extremely high stability (only 3.71% increase of potential after 100 h test and no current decay after cyclic voltammetry of 31,000 cycles). The outstanding performance can be attributed to the in-situ electrochemical activation induced surface reconstruction to form a stable oxyhydroxide surface layer, the cocktail effect (multi-metal synergy) brought by high entropy, and the advantages of amorphous structure itself. The outstanding catalytic properties of the new high-entropy amorphous metal oxide, as well as its advantages of low cost and simple preparation, suggest its great potential in water splitting.

Covalent Pinning of Highly Dispersed Ultrathin Metallic-Phase Molybdenum Disulfide Nanosheets on the Inner Surface of Mesoporous Carbon Spheres for Durable and Rapid Sodium Storage.

Two-dimensional (2D) transition-metal dichalcogenide materials show potential for use in alkali metal ion batteries owing to their remarkable physical and chemical properties. Nevertheless, the electrochemical energy storage performance is still impaired by the tendency of aggregation, volume, and morphological change during the conversion reaction and poor intrinsic conductivity. Until now, ultrathin molybdenum disulfide nanosheets with a metallic-phase structure on the inner surface of mesoporous hollow carbon spheres (M-MoS2@HCS) have rarely been investigated as an anode for sodium-ion batteries. In this work, a novel M-MoS2@HCS anode was designed and synthesized by employing a template-assisted solvothermal reaction. Structural and chemical analyses indicate that the M-MoS2 nanosheets with a larger interlayer spacing compared to their semiconductor counterpart grow on the inner surface of HCS via covalent interactions. When used as the anode materials for Na+ storage, the M-MoS2@HCS anode presents durable and rapid sodium storage properties. The developed electrode shows a reversible capacity of 291.2 mAh g-1 at a high current density of 5 A g-1. After 100 cycles at 0.1 A g-1, the reversible capacity is 401.3 mAh g-1 with a capacity retention rate of 79%. After 2500 cycles at 1.0 A g-1, the electrode still delivers a reversible capacity of 320.1 mAh g-1 with a capacity retention rate of 75%. The excellent sodium storage capability of the MoS2@HCS electrode is explained by the special structural design, which reveals great potential to accelerate the practical applications of transition-metal dichalcogenide electrodes for sodium storage.