High-performance Rechargeable Batteries Research Articles

A Bifunctional Iron-Nickel Oxygen Reduction/Oxygen Evolution Catalyst for High-Performance Rechargeable Zinc-Air Batteries.

Efficient and robust electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial for fuel cells, metal-air batteries, and other energy technologies. Here, a highly stable, efficient bifunctional OER/ORR electrocatalyst (FeNi-NC@MWCNTs) is reported and demonstrated its integration and robust performance in an aqueous Zinc-air battery (ZAB). The catalyst is based on neighboring iron/nickel sites (FeNiN6) which are atomically dispersed on porous nitrogen-doped carbon particles. The particles are wrapped in electrically conductive multi-walled carbon nanotubes for enhanced electrical conductivity. Electrocatalytic analyses show high OER and ORR performance (OER/ORR voltage difference = 0.69V). Catalyst integration in a ZAB results in excellent performance metrics, including an open circuit voltage of 1.44V, a specific capacity of 782 mAh g-1 (at j = 15mA cm-2), a peak power density of 218mW cm-2 (at j = 260mA cm-2) and long-term durability over 600 charge/discharge cycles. Combined experimental and theoretical (density functional theory) analyses provide an in-depth understanding of the physical and electronic structure of the catalyst and the role of the FeNi dual atom reaction site. The study therefore provides critical insights into the structure and reactivity of high-performance bifunctional OER/ORR catalysts based on atomically dispersed non-critical metals.

Synthesis-Structure-Property of High-Entropy Layered Oxide Cathode for Li/Na/K-Ion Batteries.

Increasing demand for rechargeable batteries necessitates improvements in electrochemical performance. Traditional optimal approaches such as elemental doping and surface modification are insufficient for practical applications of the batteries. High-entropy materials (HEMs) possess stable solid-state phases and unparalleled flexibility in composition and electronic structure, which facilitate rapid advancements in battery materials. This review demonstrates the properties of HEMs both qualitatively and quantitatively, and the mechanisms of their enhancement on battery properties. It also illustrates the progress in high-entropy layered oxide cathode materials (HELOs) for lithium/sodium/potassium ion batteries (LIBs/SIBs/PIBs) in the perspectives of synthesis, characterization and application, and elucidating the synthesis-structure-property relationship. Furthermore, it outlines future directions for high-entropy strategies in battery study: precise synthesis control, understanding of reaction mechanisms through structural characterization, elucidation of structure-performance correlations, and the computational and experimental methods integration for rapid screening and analysis of HEMs. The perspective aims to inspire researchers in the development of high-performance rechargeable batteries.

Anti-swelling gel polymer electrolyte membrane for high-performance lithium-ion battery

Gel polymer electrolyte (GPE) represents an effective and advanced substitution of polyolefin separator in high-rate lithium-ion rechargeable batteries. We here develop a novel pyridine ionic liquid (IL)-based GPE membrane for that purpose via a one-step reactive vapor-induced phase separation (RVIPS) method. Casting mixture solution of poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) and 1-butylpyridinium hexafluorophosphate ([C4Py]PF6) to evaporate solvent in ammonia water vapor, the IL-based membrane was successfully prepared in one step. The effects of the IL content on the membrane microstructure were investigated in detail. Our results demonstrate that the pyridine IL plays a role as plasticizer to suppress crystallization of the polymer, while the RVIPS process can induce dehydrofluorination-crosslinking of PVDF-HFP to greatly reduce swelling of the membrane in liquid electrolyte. Based on those, the GPE from the membrane containing 10 % [C4Py]PF6 exhibits the best electrochemical properties (ionic conductivity of 1.48 mS cm−1, Li+ transference number of 0.66, and electrochemical stable window of 5.2V), though it uptakes a moderate amount of liquid electrolyte. Moreover, the long-term interfacial stability of the GPE with the metal anodes was checked to indicate its suitability as excellent GPE. According to the battery tests, the GPE exhibits superior discharge capacities at high C-rates, achieving 129.7 mAh g−1 at 3C and 115.5 mAh g−1 at 5C, while remains a low capacity decay of 0.014 % per cycle over 300 cycles at 3C. Therefore, our work provides a facile strategy of one-step RVIPS to prepare pyridine ionic liquid-based GPE, which demonstrates promising potential for high-performance rechargeable lithium-ion battery.

In situ reconstruction of bimetallic heterojunctions encapsulated in N/P co-doped carbon nanotubes for long-life rechargeable zinc-air batteries

Efficient and stable bifunctional electrocatalysts are crucial for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in high-performance rechargeable zinc-air batteries (ZABs). Despite significant advancements in non-noble metal-based catalysts over the past decades, the rational tuning of various active materials for efficient ORR and OER, along with the identification of genuine active sites, remains a formidable challenge. Encouraged by the development of in-situ characterization technologies, research on bifunctional catalysts for ZABs has gradually shifted to exploring the true active sites and investigating catalyst evolution and degradation, which is vital for further breakthroughs in bifunctional catalysts. In this study, we developed a facile method to encapsulate bimetallic heterojunction CoFe/CoFeP in N/P co-doped carbon nanotubes (CNTs) as a bifunctional catalyst for ZABs. This unique heterojunction structure prevents the dissolution and erosion of transition metals, enhances continuous electron transfer and mass transport, and effectively boosts the catalyst's bifunctional activity and stability. Importantly, ex-situ and in-situ techniques were employed to track the dynamic ORR and OER catalytic processes, capture the reconstructions of bifunctional catalysts, and reveal the real active sites. The CoFe/CoFeP@NPC catalyst exhibits superior bifunctional catalytic activity and stability, especially with a half-wave potential of 0.887 V for ORR and 1.55 V at 10 mA cm−2 for OER. Impressively, the assembled rechargeable ZABs demonstrate a high-power density (550 mW cm−2), a low charge-discharge voltage difference (0.7 V), and ultralong cycling for over 1600 h.

Xiaoli Dong.

"The most important factor in the choice of my current research topic was the urgent demand for high-performance rechargeable batteries to face the low-temperature scenarios… I advise my students to remain open-minded, think outside the box and look at problems from a third-person perspective…" Find out more about Xiaoli Dong in her Introducing… Profile.

Review and prospect on Metal-organic framework-based Separators for Lithium–Sulfur Battery

With the continuous advancement of technology, wearable smart devices and electric vehicles (EVs) have become an integral part of our daily lives. The increasing demand for energy from these devices and vehicles has driven the pursuit of high-performance rechargeable battery technology. In particular, the widespread adoption of electric vehicles has set higher standards for the energy density and cycle life of batteries. However, the energy density of the widely used lithium-ion batteries is currently limited by the theoretical capacity of commercial cathode materials, and there are certain challenges in terms of safety and cost-effectiveness. Therefore, the development of a new generation of rechargeable batteries with higher energy density, better safety, and more economical cost is particularly urgent. Lithium-sulfur batteries, due to their high energy density, high economic benefits, and high environmental friendliness, are considered to be one of the most promising successors to the widely used lithium-ion batteries. However, in practical applications, the electrochemical performance of lithium-sulfur batteries still needs to be improved. In particular, the poor conductivity of sulfur/lithium and the shuttle effect of polysulfides make the cycle life of the battery less than ideal, and lithium-sulfur batteries (LSB) are still far from achieving large-scale commercialization. The separator used in lithium-sulfur batteries plays a crucial role in its cycle performance and safety. The current commercial separator lacks the ability to effectively regulate the shuttle of polysulfides and is prone to thermal runaway at high temperatures. Therefore, to improve these issues, various functional materials have been used to modify the separator. Among them, as a new type of porous coordination polymer, metal organic frameworks (MOFs) have become a promising material for modifying separators due to their large specific surface area and highly ordered tunable nano-holes.At the same time, their rich inorganic nodes and designable organic ligands allow for the customization of pore chemistry at the molecular level, which can interact with the electroactive components in lithium-sulfur batteries in a tunable manner. This article reviews the reaction mechanism of lithium-sulfur batteries and the structural advantages of MOFs in terms of pore chemistry and morphology and briefly introduces the research progress of MOF-based interfacial layers for the functionalization of LSB separators in recent years. It elaborates on the mechanisms by which various modified separators improve electrochemical performance and provides a prospect for the development prospects of the field.

Enhanced electrochemical performance of garnet Li7La3Zr2O12 electrolyte by efficient incorporation of LiCl

Garnet-type Ta-doped Li7La3Zr2O12 (LLZO) lithium-ion-conducting ceramic electrolytes has become the promising and critical candidate for developing the high-energy-density all-solid-state lithium batteries, due to the satisfied Li+ conductivity, stability against metallic lithium anode, and the feasible preparation under ambient air. Here, to further increase the lithium-ion conductivity of LLZO comparable to that of the commercial organic liquid electrolytes, lithium chloride (LiCl) is effectively introduced to synthesize the garnet-type ceramic electrolytes with the nominal composition (Li6.5La3Zr1.5Ta0.5O12)1-x–(LiCl)x (x = 0, 5mol%, 10mol%, 15mol%, 20mol%, and 25mol%) via high-temperature calcination process. The cubic structure with highly conductive performance is confirmed from X-ray diffraction measurement as well as Raman spectra analysis. Structural information is observed according to field emission scanning electron microscope equipped with energy dispersive spectrometer and density measurements. Among above investigated ceramic compositions, the prepared (Li6.5La3Zr1.5Ta0.5O12)0.85–(LiCl)0.15 ceramic electrolyte sheet sintered at 1200 °C for 12h presents the room-temperature Li-ion conductivity of 1.22 × 10−3 S·cm−1 by alternating current (AC) impedance analysis along with the corresponding activation energy of 0.262eV through Arrhenius equation calculation. The electronic conductivity measurements are also done by direct-current polarization to confirm the ionic nature for all investigated ceramics. Furthermore, the Li|(Li6.5La3Zr1.5Ta0.5O12)0.85–(LiCl)0.15 |Li symmetric batteries can possess the small interfacial resistance of 92.3 Ω cm2 and stably run for 1000 h at 0.1 mA cm−2 without a short circuit at room temperature. The hybridized lithium-sulfur battery with (Li6.5La3Zr1.5Ta0.5O12)0.85–(LiCl)0.15 electrolyte delivered excellent initial room-temperature discharge capacity of 1204mAh·g−1 and 1152 mAh·g−1 under the current density of 0.1C and 0.2C respectively, large coulombic efficiency, and great cycling stability. Moreover, the lithium-sulfur batteries also can show excellent cycling performances under different current densities and a good capacity recoverability. The above investigation results suggest that the low-melting-point LiCl incorporation in Li6.5La3Zr1.5Ta0.5O12 electrolyte is an effective measurement to synthesize the cubic and dense Li-stuff garnet ceramic sheets for the high-performance rechargeable next-generation solid-state batteries.

WN-CoS2 nanoparticles encapsulated into carbon nanotubes enable a stable and high-performance rechargeable zinc air battery

The battery performance associated with longevity are the priorities for the industrialization of rechargeable zinc air battery (ZAB). Herein, we have reported the construction of WN-CoS2 heterostructure enveloped by nitrogen and phosphorus co-doped carbon nanotubes (WN-CoS2@NPCNT). WN-CoS2@NPCNT performs a superior oxygen evolution reaction (OER) catalytic activity of 279 mV overpotential to reach 10 mA cm−2, lowered by 85 mV with relative to CoS2@NCNT attributing to the heterostructure efficiently modulating the electronic structure of active sites. Besides, the half-wave potential reaches 0.875 V vs. RHE for WN-CoS2@NPCNT under oxygen reduction reaction (ORR) condition, corresponding to a 3.2-time higher kinetic current density compared to commercial Pt/C. Due to the exceptional bifunctionality, the battery performance is 205 mW cm−2 for WN-CoS2@NPCNT, 1.54 times higher than commercial counterpart, Pt/C + IrO2. Impressively, the battery performance sustains for 1000 h for WN-CoS2@NPCNT stemming from the confinement effect caused by NPCNT. In addition, the all-solid-state ZAB shows a high-power density of 55 mW cm−2.

Plasma-engineering of Pt-decorated NiCo2O4 nanowires with rich oxygen vacancies for enhanced oxygen electrocatalysis and zinc-air battery performance

The development of low-cost and efficient bifunctional catalysts is of great importance for the advancement of high-performance rechargeable zinc-air batteries. In this study, we present a composite material comprising Pt-decorated NiCo2O4 nanowires enriched with abundant oxygen vacancies, designed as an excellent bifunctional electrocatalyst for both the oxygen evolution reaction and the oxygen reduction reaction. The introduction of Pt atoms and oxygen vacancies onto the NiCo2O4 nanowires was achieved with the assistance of plasma treatment. This approach resulted in a catalyst with a greater number of active sites, enhanced surface conductivity and significantly improved electrocatalytic activity compared to the original NiCo2O4 nanowires. Moreover, the zinc-air battery based on this composite catalyst exhibits a narrow charge/discharge voltage gap and superior stability, which is better than batteries employing commercial noble-metal-based catalysts. This work provides a rational strategy for the construction of high-active and cost-effective Pt-based electrocatalysts.

Surface engineering of TiSiO4 nano-coating for high-voltage nickel-rich ternary cathodes: An approach to improve cyclic performance

In recent years, layered ternary transition metal oxides with a high nickel content have gained substantial attention as a potential positive electrode material for lithium-ion batteries. However, its poor rate capability, cyclability, and capacity retention at high working voltages limit its use in commercial lithium-ion batteries. To overcome these challenges, we synthesize a cost-effective wet-chemical deposition of novel TiSiO4 nano-coatings over the surface of LiNi0.83Mn0.06Co0.11O2 (NMC-83). X-ray diffraction and electron microscopy confirm the presence of a coating and verify that the deposition process did not alter the crystallinity and morphology of the NMC-83 particles. In addition, during cycling, it completely protects NMC-83 with enhancements in hexagonal phase transitions between H2 and H3, resulting in excellent cycling stability at upper cut-off voltages. Likewise, when the amount of coated material is equal to 1 wt%, it provides faster ion kinetics and a stable electrode-electrolyte interface. The 1 wt% TiSiO4 coating provides 35 % retention after 250 cycles at a 0.5C rate, while the pristine NMC-83 shows only 13.7 %. From postmortem analysis, the 1 wt% TiSiO4-coated NMC-83 cathode maintains its stable polycrystalline nature compared with pristine NMC-83. Thus, this novel TiSiO4 nanocoating has significant implications for developing high-performance rechargeable batteries for energy applications.

Anion vacancy engineering in carbon coating VS4 microspheres assembled by nanorod arrays for high-performance rechargeable Mg-Li hybrid batteries

Transition metal sulfides (TMSs) stand out as promising cathodes for rechargeable Mg-Li hybrid ion batteries (MLIBs) owing to their high theoretical capacity and rich redox chemistry. Nevertheless, it still faces great challenges involving the sluggish reaction kinetics and insufficient active sites, resulting in unsatisfactory stability and limited rate capability. And the role of anion vacancies on improving electrochemical properties of TMSs is still unclear. Herein, we have successfully designed an anion defect engineering strategy for the construction of carbon coating VS4 microspheres assembled by nanorod arrays (Sv-VS4@C-300) as the high-performance cathode for MLIBs. The systematic electrochemical tests together with theoretical calculations reveal that the sulfur vacancies simultaneously improve ion adsorption ability, facilitate charge transfer rate and boost reaction kinetics. Additionally, the open microsphere structure together with rich sulfur vacancies cooperatively provide more active sites and release the internal stress during cycling, thereby realizing the enhancement of capacity and structural stability. Consequently, these features enable Sv-VS4@C-300 with impressively high reversible capacity (485.1 mAh/g at 50 mA g−1) and exceptional long cycle lifespan (128.3 mAh/g at 2000 mA g−1 after 5000 cycles). This work implements an innovative strategy represented by anion vacancy engineering in the design of high-performance TMSs-based cathodes for rechargeable batteries.

Regulating the Double-Way Traffic of Cations and Anions in Ambipolar Polymer Cathodes for High-Performing Aluminum Dual-Ion Batteries.

The strong Coulombic interactions between Al3+ and traditional inorganic crystalline cathodes present a significant obstacle in developing high-performance rechargeable aluminum batteries (RABs) that hold promise for safe and sustainable stationary energy storage. While accommodating chloroaluminate ions (AlCl4 -, AlCl2+, etc.) in redox-active organic compounds offers a promising solution for RABs, the issues of dissolution and low ionic/electronic conductivities plague the development of organic cathodes. Herein, electron donors are synthetically connected with acceptors to create crosslinked, bipolar-conjugated polymer cathodes. These cathodes exhibit overlapped redox potential ranges for both donors and acceptors in highly concentrated AlCl3-based ionic liquid electrolytes. This approach strategically enables on-site doping of the polymer backbones during redox reactions involving both donor and acceptor units, thereby enhancing the electron/ion transfer kinetics within the resultant polymer cathodes. Based on the optimal donor/acceptor combination, the bipolar polymer cathodes can deliver a high specific capacity of 205mAhg-1 by leveraging the co-storage of AlCl4 - and AlCl2+. The electrodes exhibit excellent rate performance, a stable cycle life of 60000 cycles, and function efficiently at high mass loadings, i.e., 100mg cm-2, and at low temperatures, i.e., -30°C. The findings exemplify the exploration of high-performing conjugated polymer cathodes for RABs through rational structural design.

Facilitating charge transfer via a Semi-Coherent Fe(PO3)2-Co2P2O7 heterointerface for highly efficient Zn-Air batteries

Developing reversible oxygen electrodes for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is crucial for achieving high-performance rechargeable Zn-air batteries (ZABs). This study introduced an nitrogen-doped carbon confined with a semi-coherent Fe(PO3)2-Co2P2O7 heterojunction for bifunctional oxygen electrocatalysis. This nanocomposite yielded an ORR half-wave potential of 0.908 V and an OER overpotential of 291 mV at 10 mA/cm2. ZABs incorporating this catalyst yielded impressive performance, including a peak power density of 203 mW/cm2, a specific capacity of 737 mAh/gZn, and promoted stability. Both experimental and theoretical simulations demonstrated that the unique electric field between Fe(PO3)2 and Co2P2O7 promoted efficient charge transport across the heterointerface. This interaction likely modulated the d-band center of the heterojunction, expedite the desorption of oxygen intermediates, thus improving oxygen catalysis and, consequently, ZAB performance. This work illustrates a significant design principle for creating efficient bifunctional catalysts in energy conversion technologies.

A Facile Strategy for Constructing High-Performance Polymer Electrolytes via Anion Modification and Click Chemistry for Rechargeable Magnesium Batteries.

Polymer electrolytes play a crucial role in advancing rechargeable magnesium batteries (RMBs) owing to their exceptional characteristics, including high flexibility, superior interface compatibility, broad electrochemical stability window, and enhanced safety features. Despite these advantages, research in this domain remains nascent, plagued by single preparation approaches and challenges associated with the compatibility between polymer electrolytes and Mg metal anode. In this study, we present a novel synthesis strategy to fabricate a glycerol α,α'-diallyl ether-3,6-dioxa-1,8-octanedithiol-based composite gel polymer electrolyte supported by glass fiber substrate (GDT@GF CGPE) through anion modification and thiol-ene click chemistry polymerization. The developed route exhibits novelty and high efficiency, leading to the production of GDT@GF CGPEs featuring exceptional mechanical properties, heightened ionic conductivity, elevated Mg2+ transference number, and commendable compatibility with Mg anode. The assembled modified Mo6S8||GDT@GF||Mg cells exhibit outstanding performance across a wide temperature range and address critical safety concerns, showcasing the potential for applications under extreme conditions. Our innovative preparation strategy offers a promising avenue for the advancement of polymer electrolytes in high-performance rechargeable magnesium batteries, while also opens up possibilities for future large-scale applications and the development of flexible electronic devices.

Tailored crystal planes of VO2 cathode power fast Zn2+ storage

Vanadium dioxide (VO2) cathode with specific tunnel structure and favorable specific capacity is critical for developing aqueous zinc-ion batteries (AZIBs) with excellent electrochemical performance. However, sluggish electrochemical kinetics hampered its development in burgeoning energy storage devices. Herein, we tailored VO2 material with different exposed crystal planes and employed as cathodes for AZIBs. The comprehensive analyses indicate the exposed (201) and (001) crystal planes are favorable for fast electrochemical kinetics, high capacitance storage, and the smallest diffusion energy barrier, which guarantee electrodes with high discharge capacity (367 mA h/g at 0.1 A/g), excellent rate capability (281 mA h/g at 4 A/g) and cycling stability over 800 cycles. Besides, Ex-situ characterizations manifest VO2 cathode with specific exposed crystal planes easily transformed to Zn3+x(OH)2V2O7·2H2O in the first discharge process, hence allowing continuous embedding of Zn2+ in this layered structure, and the ex-situ scanning electron microscopy (SEM) analysis confirms the morphology change matched well with the structural transformation. This study may enlighten and promote the role of exposed crystal plane to develop high-performance rechargeable batteries.

Cu Regulating the Bifunctional Activity of Co-O Sites for the High-Performance Rechargeable Zinc-Air Battery.

The rational design of cost-effective and highly active electrocatalysts becomes the crucial energy storage technology to boost the kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), which hinders the large-scale application of metal-air batteries under the situation of increasingly pressing energy anxiety. Herein, the Co-based ZIF introduced the moderate amount of Cu2+-derived Cu/Co metal nanoparticles (NPs) embedded in carbon frameworks after high-temperature calcination. The Co-O bond on the surface of Co nanoparticles is modulated by adjacent Cu nanoparticles with the surface Cu-O bonds. The resulted increase of the Co2+/Co3+ ratio in 0.1CuCo-NC enhances the ORR/OER bifunctional catalytic kinetics along with the ΔE of 0.639 V. In situ Raman spectra of the catalyst on the three-electrode system as well as in the driven zinc-air battery (ZAB) show that the Co-O active sites regulated by Cu nanoparticles with Cu-O bonds maintain a periodic lattice expansion and compression during discharging and charging. The zinc-air battery based on 0.1CuCo-NC has a peak power density of up to 198.3 mW cm-2, a mass-specific capacity of 798.2 mAh g-1, and a cycling stability of 923 h at room temperature. This work makes up the research gap of a Co-based metal-organic framework (MOF)-derived catalyst regulated by a transition metal.

High performance rechargeable aluminium ion batteries enabled by full utilization and understanding of polyaniline cathodes

As a renowned conductive polymer, polyaniline (PANI) shows remarkable potential in organic cathode materials for rechargeable aluminium ion batteries (RAIBs). However, existing research has not given sufficient understanding and explanation of the structure and states of PANI but failed to achieve ideal electrochemical performance. In this study, we differentiate and investigate for the first time its primary-doped (PANI-1), re-doped (PANI-Re), secondary-doped (PANI-2), and emeraldine based (PANI-EB) forms, meanwhile attempt to enhance the conductivity of PANI-EB using multi-walled carbon nanotubes (PANI-EB@C). Among them, the high-doped PANI-2 and non-doped PANI-EB exhibit theoretical capacity utilization far superior to lower doped PANI-1 and PANI-Re, with both specific capacities reaching approximately 225 mAh/g (full capacity utilization rate of 76.53 %) at a current density of 1 A/g, while maintaining capacity retention rates of 92.89 % after 2000 cycles and 92.44 % after 5000 cycles, respectively. Furthermore, the high-conductivity PANI-EB@C displays a discharge specific capacity of 284 mAh/g (full capacity utilization rate of 96.59 %), with a capacity retention rate of 91.19 % after 5000 cycles. Electrochemical analysis, Gaussian theoretical calculations, ex-situ characterization collectively indicate that the electrochemical performance of doped PANI is positively correlated with the degree of doping-induced conductivity changes, while the unique internal redox process of PANI-EB enhances the release of performance and could be further optimized by the assistant of conductivity medium. This work advances the classification of the electrochemical performance and structural understanding of PANI cathode materials to an extremely high stage, towards the practical application of a low-cost, high-performance, sustainable, and green cathode material in large-scale energy storage devices.

Three-dimensional mixed-valence polyoxovanadates@polyaniline architecture towards high-performance rechargeable aqueous zinc-ion batteries cathode

Aqueous zinc ion batteries (AZIBs) are toward promising candidates of energy storage systems for their low cost, high safety and eco-friendliness, whereas the sluggish reaction kinetics and unstable internal structure of cathode materials greatly limited the practical application of AZIBs. Herein, we employ the three-dimensional mixed-valance polyoxovanadates [Co3(H2O)12][VIV10VV8O42(SO4)]·24H2O (CoVO) coated with polyaniline (PANI) as stable zinc ion storage material (denoted as CoVO@PANI). The 3D highly porous CoVO framework constructs multidimensional interconnected Zn2+ migration channels, and the high conductivity of PANI facilitates the formation of oxygen defects during in-situ polymerization process and inhibits the polyoxovanadates dissolution. Density functional theory calculation reveals that PANI significantly regulates the electronic property of the CoVO host, further promoting the electron/ion transfer kinetics and thus contributing to high-effciency Zn2+ storage performance. As expected, the optimized as-fabricated CoVO@PANI60 cathode exhibits a high reversible capacity of 456.8 mAh g−1 at 0.1 A g−1 and long-term cyclability with capacity retention of 90.4 % after 1500 cycles at 10 A g−1.

Polyoxomolybdate-Based Metal-Organic Framework-Derived Cu-Embedded Molybdenum Dioxide Hybrid Nanoparticles as Highly Efficient Electrocatalysts for Al-S Batteries.

High-performance rechargeable aluminum-sulfur batteries (RASB) have great potential for various applications owing to their high theoretical capacity, abundant sulfur resources, and good safety. Nevertheless, the practical application of RASB still faces several challenges, including the polysulfide shuttle phenomenon and low sulfur utilization efficiency. Here, we first developed a synergistic copper heterogeneous metal oxide MoO2 derived from polymolybdate-based metal-organic framework as an efficient catalyst for mitigating polysulfide diffusion. This composite enhances sulfur utilization and electrical conductivity of the cathode. DFT calculations and experimental results reveal the catalyst Cu/MoO2@C not only effectively anchors aluminum polysulfides (AlPSs) to mitigate the shuttle effect, but also significantly promotes the catalytic conversion of AlPSs on the sulfur cathode side during charging and discharging. The unique nanostructure contains abundant electrocatalytic active sites of oxide nanoparticles and Cu clusters, resulting in excellent electrochemical performance. Consequently, the established RASB exhibits an initial capacity of 875 mAh g-1 at 500 mA g-1 and maintains a capacity of 967 mAh g-1 even at a high temperature of 50 °C.

Ternary Mg alloy-based artificial interphase enables high-performance rechargeable magnesium batteries

Rechargeable magnesium batteries (RMBs) provide potential advantages over lithium-ion batteries in terms of high volumetric capacity, natural abundance, and high safety. However, the rational design of high-performance magnesium-based metal anodes compatible with conventional electrolytes is a big challenge for the viability of RMBs. In this work, an in-situ formed ternary alloy-based artificial interphase layer on Mg foil as an anode was successfully prepared through a facile and universal electrodeposition strategy. The Mg-Sn-Bi@Mg anode provides high charge transfer dynamics for Mg deposition and constructs a reduced energy barrier for Mg2+ ions desolvation. Thanks to the unique Mg deposition behaviors, the Mg-Sn-Bi@Mg alloy anode demonstrates a low overpotential of 39.4 mV and a long cycle life of >2000 h. The transfer kinetics for RMBs can be largely improved due to the unique alloying reactions. Density functional theory (DFT) calculations demonstrate that the designed ternary alloy-based artificial interphase layer enables faster Mg2+ ion migration than the bare Mg electrode. Full cells with Mo6S8 cathode also show ultra-stable cycling performance over 2400 cycles at 1C in a conventional all-phenyl complex (APC) electrolyte. This facile interface modification strategy sheds light on the development of advanced RMBs and also provides a promising direction for the design of high-performance Mg-based alloy anodes for high-performance RMBs and beyond.