Magnesium Batteries Research Articles

Recent Advances in Electrolytes for Magnesium Batteries: Bridging the gap between Chemistry and Electrochemistry.

Rechargeable magnesium batteries (RMBs) have the potential to provide a sustainable and long-term solution for large-scale energy storage due to high theoretical capacity of magnesium (Mg) metal as an anode, its competitive redox potential (Mg/Mg2+:-2.37 V vs. SHE) and high natural abundance. To develop viable magnesium batteries with high energy density, the electrolytes must meet a range of requirements: high ionic conductivity, wide electrochemical potential window, chemical compatibility with electrode materials and other battery components, favourable electrode-electrolyte interfacial properties and cost-effective synthesis. In recent years, significant progress in electrolyte development has been made. Herein, a comprehensive overview of these advancements is presented. Beginning with the early developments, we particularly focus on the chemical aspects of the electrolytes and their correlations with electrochemical properties. We also highlight the design of new anions for practical electrolytes, the use of electrolyte additives to optimize anode-electrolyte interfaces and the progress in polymer electrolytes.

Revolutionizing Battery Longevity by Optimising Magnesium Alloy Anodes Performance

This research explores the enhancement of electrochemical performance in magnesium batteries by optimising magnesium alloy anodes, explicitly focusing on Mg-Al and Mg-Ag alloys. The study’s objective was to determine the impact of alloy composition on anode voltage stability and overall battery efficiency, particularly under extended cycling conditions. The research assessed the anodes’ voltage behaviour and internal resistance across magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) electrolyte formulations using a systematic setup involving cyclic voltammetry on the anode and electrochemical impedance spectroscopy. The Mg-Al alloy demonstrated superior performance, with minimal voltage drop and lower resistance increase than the Mg-Ag alloy. The results showed that the Mg-Al alloy maintained over 85% energy efficiency after 100 cycles, significantly outperforming the Mg-Ag alloy, which exhibited increased degradation and efficiency reduction to approximately 80%. These findings confirm that incorporating aluminium into magnesium anodes stabilises the anode voltage and enhances the overall battery efficiency by mitigating degradation mechanisms. Consequently, the Mg-Al alloy is identified as an up-and-coming candidate for use in advanced battery technologies, offering energy density and cycle life improvements. This study lays the groundwork for future research to refine magnesium alloy compositions further to boost battery performance.

Regulating Electric Double Layer via Self‐Assembled Monolayer for Stable Solid/Electrolyte Interphase on Mg Metal Anode

Modulating the cationic solvation structure with high donor‐number (DN) additive is an effective strategy to construct a stable solid electrolyte interphase (SEI) on the Mg anode, which necessitates meticulous consideration of electrolyte chemistry and substantial quantities of additives. Notably, the electric double layer (EDL) adjacent to anode is pivotal role in SEI formation yet remains understudied. In this study, we propose a novel self‐assembled monolayer (SAM) strategy by utilizing (trifluoromethyl)trimethylsilane (TFTMS, only 2 vol%, 1.4 mol%, 0.135 mol L‐1), a low DN but strong Mg metal absorbability through electron‐withdrawing groups(−CF3), to modulate the complex structure of the Helmholtz absorption plane. Through dipole−dipole interaction between the electronegative fluorine (−CF3 of TFTMS) and electropositive hydrogen (−CH3/−CH2 of solvents), TFTMS weakens solvent−Mg2+ coordination and thus enhances anion−Mg2+ interaction, inducing a stable and dense SEI with superior electronic insulation to realize horizontal Mg plating/stripping. Consequently, the designed electrolytes enable the symmetric cells to cycle stable for up to 1000 hours and reversible Mg plating/stripping under 5 mA cm‐2, they show favorable compatibility with various cathodes. More importantly, the SAM strategy has good generality in other electrolyte systems, demonstrating a simple and effective route to promote the practical application of rechargeable magnesium battery.

Coupling Manipulation of Interfacial Chemistry and Coordination Structure in Vanadium Oxides Enables Rapid Magnesium Ion Diffusion Kinetics

AbstractRechargeable magnesium batteries (RMBs) are a highly promising energy storage system due to their high volumetric capacity and intrinsic safety. However, the practical development of RMBs is hindered by the sluggish Mg2+ diffusion kinetics, including at the cathode‐electrolyte interface (CEI) and within the cathode bulk. Herein, we propose an efficient strategy to manipulate the interfacial chemistry and coordination structure in oligolayered V2O5 (L−V2O5) for achieving rapid Mg2+ diffusion kinetics. In terms of the interfacial chemistry, the specific exposed crystal planes in L−V2O5 possess strong electron donating ability, which helps to promote the degradation dynamics of C−F/C−S bonds in the electrolyte, thereby establishing the inorganic‐organic interlocking CEI layer for rapid Mg2+ diffusion. In terms of the coordination structure, the straightened V−O structure in L−V2O5 provides efficient ions diffusion path for accelerating Mg2+ diffusion in the cathode. As a result, the L−V2O5 delivers a high reversible capacity (355.3 mA h g−1 at 0.1 A g−1) and an excellent rate capability (161 mAh g−1 at 1 A g−1). Impressively, the interdigital micro‐RMBs is firstly assembled, exhibiting excellent flexibility and practicability. This work gives deeper insights into the interface and interior ions diffusion for developing high‐kinetics RMBs.

3D Tunnel Copper Tetrathiovanadate Nanocube Cathode Achieving Ultrafast Magnesium Storage Reactions through a Charge Delocalization and Displacement Mechanism.

Rechargeable magnesium batteries are attractive candidates for large-scale energy storage applications because of the low cost and high safety, but the scarcity and inferior performance of the cathode materials are hindering the development. In the present study, a kind of copper tetrathiovanadate (Cu3VS4) cathode is designed and developed with a comprehensive consideration of the chemical and electronic structures. The vanadium and sulfur atoms form chemical bonds with high covalent proportion, facilitating electron delocalization via the vanadium-sulfur bonds. This reduces the interaction with the bivalent magnesium cation and induces the coredox of vanadium and sulfur. The crystal structure of Cu3VS4 has interlaced 3D tunnels for solid-state magnesium cation transport. The Cu3VS4 cathode shows a high capacity of 350 mA h g-1 at 100 mA g-1, an outstanding rate performance of 67 mA h g-1 at 10 A g-1, and stable cycling for 1000 cycles at 5 A g-1 without obvious capacity fading. Prominently, a high areal mass load of 3.5 mg cm-2 could be achieved without obvious rate capability decay, which is quite favorable to pair with the high-capacity magnesium metal anode in practical application. The mechanism investigation and theoretical computation demonstrate that Cu3VS4 undergoes first a magnesium intercalation and then a displacement reaction, during which the crystal structure is maintained, assisting the reaction reversibility and cycling stability. All the copper, vanadium, and sulfur elements experience redox and contribute to the high capacity. Moreover, the weakened interaction with magnesium cations, well-kept 3D cation transport tunnels, and high electronic conductivity result in the superior rate performance and high areal active material loading. The present study develops a high-performance cathode for rechargeable magnesium batteries and reveal the design principle based on both of chemical and electronic structures.

High-capacity, fast-charging and long-life magnesium/black phosphorous composite negative electrode for non-aqueous magnesium battery

Secondary non-aqueous magnesium-based batteries are a promising candidate for post-lithium-ion battery technologies. However, the uneven Mg plating behavior at the negative electrode leads to high overpotential and short cycle life. Here, to circumvent these issues, we report the preparation of a magnesium/black phosphorus (Mg@BP) composite and its use as a negative electrode for non-aqueous magnesium-based batteries. Via in situ and ex situ physicochemical measurements, we demonstrate that Mg ions are initially intercalated in black phosphorus two-dimensional structures, forming chemically stable MgxP intermediates. After the formation of the intermediates, Mg electrodeposition reaction became the predominant. When tested in the asymmetric coin cell configuration, the Mg@BP composite electrode allowed stable stripping/plating performances for 1600 h (800 cycles), a cumulative capacity of 3200 mAh cm−2, and a Coulombic efficiency of 99.98%. Assembly and testing of the Mg@BP | |nano-CuS coin cell enabled a discharge capacity of 398 mAh g−1 and an average cell discharge potential of about 1.15 V at a specific current of 560 mA g−1 with a low decay rate of 0.016% per cycle for 225 cycles at 25 °C.

Experimental and computational insights into oxygen vacancy-rich MoO2-x/N-doped carbon nanowires as high-performance cathode for magnesium batteries and magnesium-lithium hybrid batteries

This work aims to develop efficient cathode materials for magnesium based batteries, which are considered promising next-generation energy storage and conversion devices. One major challenge in magnesium based batteries is the strong Coulomb interaction between magnesium ions and cathode materials, which hinders ion storage and diffusion. To overcome this, we designed and synthesized oxygen vacancy-rich MoO2-x/N-doped carbon nanowires (MoO2-x-NC-NWS). The materials were prepared through a controlled synthesis process, ensuring the incorporation of N-doped carbon and oxygen vacancies, which play crucial roles in improving magnesium ion diffusion and storage. The prepared MoO2-x-NC-NWS demonstrated superior energy storage performance, achieving a capacity of 64 mAh/g in magnesium batteries and 263 mAh/g in magnesium-lithium hybrid batteries at a current density of 50 mA/g. Theoretical calculations further confirmed that oxygen vacancies enhance the diffusion capabilities of magnesium and lithium ions, thereby improving the overall energy storage performance. Therefore, the controllable synthesis of defects such as oxygen vacancies and the development of composite cathode materials are clearly effective strategies for enhancing the performance of magnesium-based battery cathodes. Meanwhile, this rational design of MoO2-based nanostructures provides valuable insights into the development of high-performance cathode materials for magnesium-based energy storage systems.

Constructing dilute Mg-1.0In binary alloy: A pathway to enhanced anode performance in Mg-air battery

Magnesium anode is a critical material in Mg-air battery; however, the contradiction between mitigating self-corrosion and promoting activation poses a significant obstacle to the rapid advancement of primary magnesium batteries. Herein, this issue is addressed by constructing a dilute Mg-1.0In binary alloy with 1 wt% indium as the anode material. The equiaxed dendrites and moderate indium concentration gradient in the as-cast anode facilitate the formation of a protective surface film, leading to a low corrosion rate of 0.20 mm y−1 and enhancing the stability prior to discharge. Moreover, during the battery discharge process, this unique microstructure enables the redeposition of metallic indium and indium hydroxide, thereby dramatically accelerating the shedding of oxidation products and suppressing side hydrogen evolution reaction. The Mg-1.0In anode in a Mg-air battery delivers a discharge capacity of 1587 mA h g−1 and an average voltage of 1.46 V at 10 mA cm−2, outperforming most of previously reported magnesium anodes and the control samples with various indium contents. This work would inspire the achievement of superior Mg-air battery performance through the use of binary magnesium anode system in as-cast state, as opposed to a more complex and time-consuming multi-component anode design involving heat treatment and plastic deformation.

Se-Doping on Co4S3 Cathode Based on Soft Anion Chemistry to Enhance Magnesium Storage Performance.

Rechargeable magnesium batteries (RMBs) have gradually got attention due to the high theoretical capacity, low cost and high security. However, the lack of suitable cathode materials has been a major obstacle to the development of RMBs. Transition metal sulfides (TMSs) have been studied extensively because of their high theoretical specific capacity and other advantages. However, the diffusion rate of Mg2+ in TMSs is slow and side reactions are easy to occur. In this work, soft anion doping strategy was adopted at Co4S3 cathode material. After doping the appropriate content of Se, it showed the specific capacity of 248 mAh g-1 at a current density of 100 mA g-1. The mechanism of magnesium storage was investigated by ex-situ technique. This work laid a foundation for researching cobalt-based sulfide in cathode materials of RMBs.

Polyanthraquinone with Facile Synthesis as a Cathode Material for Rechargeable Magnesium Batteries

Polyanthraquinone with Facile Synthesis as a Cathode Material for Rechargeable Magnesium Batteries

Multifunctional Water Additive Enabling Stable Cycling of Chloride‐Free Magnesium Metal Batteries Based on Carbonate Electrolyte

AbstractRechargeable magnesium batteries (RMBs) face with the challenge of interphase passivation between electrolytes and Mg anodes. Compared with ether electrolytes, carbonate solvents possess the superior electrochemical stability at cathode side, but their incompatibility with Mg metal, high viscosity, and desolvation energy barrier restrict their practical utilization in RMBs. Herein, the “unwanted‐impurity” water with high concentration is revisited and employed as multifunctional additive in carbonate electrolyte to improve the reversibility of RMBs. Water additive enables the localized deep eutectic effect, reduces the viscosity of carbonate electrolyte, and improves the Mg ion conductivity. The water molecules also participate the solvation sheath of Mg ions, resulting in the reduction of Mg deposition overpotential and inhibition of parasitic reaction. Furthermore, the co‐intercalated water molecules in V2O5 cathode layers enable the stabilization of intercalation structure and supply of additional magnesiophilic sites. Cooperated with the binder‐decorated Mg powder anode, the propylene carbonate electrolyte with water additive endows Mg||Mg symmetric cells and Mg||V2O5 full cells with satisfactory cycling performance and high‐voltage stability. This work revisits the impact of impurity water and provides a practical strategy for the utilization of conventional low‐cost carbonate electrolyte family, broadening the design and formulation of electrolytes for chlorine‐free and high‐voltage RMBs.

An ultrafast, stable and highly reversible nickel magnesium vanadate cathode for magnesium ion batteries

Rechargeable magnesium batteries are one among the strongest candidates over lithium ion batteries with abundance, cost effective and less environmental hazard. However, limitations including slow Mg2+ ion kinetics in the electrode-electrolyte interface and formation of passivating layers on the surface of magnesium metal anode affecting the rechargeable behavior of a cathode. Herein, hydrothermally synthesized NiMg2(VO4)2 nanomaterial used as cathode. The oxidation and reduction properties of Mg and V facilitates the diffusion pathway for Mg2+ and Li+ ions. Additionally, the employment of activated carbon cloth as anode diminishes the strong ionic interactions between Mg2+ ions and crystal lattice, enabling the faster diffusion of Mg2+ ions. All the electrochemical investigations are carried out at room temperature in the potential window of 1.23 V to 3.83 V against Mg/Mg2+. At a lower current density of 100 mA g−1, the specific discharge capacity have been 220 mAh g−1 for the 2nd cycle and retention of 97.1 % over 25 cycles. The specific capacity increases with more Mg2+ involvement in the reaction. At the highest current rate of 5000 mA g−1 the capacity retention is 96.8 % after 1000 cycles. Calculated energy density for a low current density is 556 Wh kg−1. The presence of multivalent V ions in the cathode reduces volume expansion, assisting charge redistribution to maintain electroneutrality. The dynamic valence property of. Vanadium ions (V2+/V5+) assist the intercalation of Mg2+ ions into the crystal lattice of cathode and possibly contribute to the highly stable and reversible discharge capacity over cycles. These findings provide a new perspective on NiMg2(VO4)2 as cathode material for magnesium ion batteries.

Self-Healable, High-Stability Anode for Rechargeable Magnesium Batteries Realized by Graphene-Confined Gallium Metal.

In this work, a self-healable, high-stability anode material for rechargeable magnesium batteries (RMBs) has been developed by introducing a core-shell structure of Ga confined by reduced graphene oxide (Ga@rGO). Via this Ga@rGO anode, a specific capacity of 150 mAh g-1 at a current of 0.5 A g-1 stable up to 1200 cycles at room temperature and a specific capacity of 100 mAh g-1 under an ultrahigh current of 1 A g-1 stable up to 700 cycles at a slightly elevated temperature of 40 °C have been achieved. Additionally, the ultrahigh rate, high-cycling stability, and long-cycle life of the anode are attributed to the stabilized structure; such a low-cost, simple, and environmentally friendly direct drop coating (DDC) method is developed to maximize the original state of the active materials. Remarkably, the self-healing ability of anodes is still presented under the ultrahigh charging current. This anode is promising for the development of high rate and high stability RMBs.

Dual‐Ion Co‐Insertion Engineering for Kinetics Enhancement and Stress Regulation in Cu3VS4 Toward Durable Magnesium/Lithium Hybrid Batteries

AbstractRechargeable magnesium batteries (rMBs) have tremendous development prospects in the field of energy storage, however, the strong electrostatic interactions induced by divalent Mg2+ give rise to the sluggish diffusion kinetics. Herein, the dual ion co‐intercalation strategy is proposed to expedite ion migration in Cu3VS4, achieving elevated specific capacity, transcendent rate capability, and ultra‐stable cycling capability. Kinetic analyses combined with DFT calculations indicate that the dual‐ion co‐insertion can fast charge transfer, reduce the diffusion barrier of Mg2+and optimize the reaction kinetics. Finite element simulations quantitatively verify that dual ion co‐intercalation contributes to alleviating magnesiation/lithiation‐induced stress in the shell layer and maintains structural integrity from a mechanical standpoint. Ex situ characterizations profoundly illustrates the multistep magnesium/lithium storage mechanisms and the evolution of structure. The proposed cation co‐intercalation strategy not only holds promise in opening new insights for high‐performance, continuously stable rMBs, but also provides inspiration for multivalent battery systems.

Mg‐Ion Conducting Gel Polymer Electrolyte Based on High Flash Point Solvent Adiponitrile for Magnesium Ion Batteries

ABSTRACTDue to some specific properties of adiponitrile (ADN) including high oxidative stability and high flash point, it is proposed as co‐solvent with an ionic liquid (IL) as a promising electrolyte solvent for application in magnesium batteries. Herein, we report a flexible film of gel polymer electrolyte (GPE) comprising a polymer poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVdF‐HFP) in which a liquid electrolyte of Mg‐trifluoromethane sulfonate (Mg‐triflate) in the mixture of ADN:IL (1‐ethyl‐3‐methylimidazolium triflate, EMITf) is immobilized for use in Mg‐batteries. The structural/morphological properties of the GPE film have been characterized via different physical techniques. The high ionic conductivity (σRT = 5.9 mS cm−1), wide potential range of oxidative stability (~4.18 V vs. Mg/Mg2+), high Mg‐ion transport number (tMg2+ = 0.67) and thermal stability up to ~160°C ascertain the compatibility of electrolyte film in magnesium batteries with high voltage cathode materials. The comparative studies of the interfacial‐stability and Mg‐stripping/plating tests on the two symmetrical cells with Mg and Mg/MWCNTs nanocomposite electrodes show the improved reversibility of the electrolyte film with Mg‐MWCNTs powder as anode material, compared with pure Mg‐powder. The overall results indicate that the GPE based on binary solvent mixture ADN:IL is high performance flexible electrolyte for Mg‐batteries with Mg‐MWCNTs powder as anode material.

Flexible magnesium-ion-conducting solid poly-blend electrolyte films for magnesium-ion batteries

Solid biodegradable polymer electrolyte systems are considered the optimal choice for energy storage devices because they are both cost-effective and energy-efficient. A solid blend polymer electrolyte (SBPE) membrane capable of transporting magnesium ions was prepared using a mixture of 70 wt% methylcellulose, 30 wt% chitosan, and varying wt% magnesium perchlorate salt. X-ray diffraction analysis revealed an increase in the amorphous nature caused by the inclusion of Mg(ClO4)2 salt in the polymer blend matrix. A Fourier transform infrared spectroscopy study of samples containing varying salt concentrations revealed secondary interactions between polymer segments and salt, which provides the basis for energy density. Moreover, through impedance analysis, it was determined that the bulk resistance decreased with increasing salt concentration. The SBPE containing 30 wt% magnesium perchlorate exhibited the highest ionic conductivity, with a value of 2.49 × 10–6 S cm−1. A comprehensive evaluation of the ion transport parameters, including mobility, carrier density, and diffusion, was conducted for the prepared electrolyte samples. Notably, an ionic transference number (tion) of approximately 0.83 was observed for the SBPE sample with 30 wt% magnesium salt, indicating ions’ prevalence as the system’s primary charge carriers. Electrochemical analyses demonstrated that the SBPE with the highest ion conductivity possessed an electrochemical stability window (ESW) of 1.92 V. Additionally, the thermal characteristics of the samples were evaluated using thermogravimetric analysis (TGA) to assess the thermal stability of the electrolyte. Finally, the highest conducting polymer electrolyte was employed to construct a primary magnesium battery, and its discharge profile with different cathode materials was studied. Based on these findings, the current study suggests an environmentally friendly, biodegradable, and economically viable electrolyte option suitable for separator cum electrolytes in magnesium-ion batteries.

Coupling Manipulation of Interfacial Chemistry and Coordination Structure in Vanadium Oxides Enables Rapid Magnesium Ion Diffusion Kinetics.

Rechargeable magnesium batteries (RMBs) are a highly promising energy storage system due to their high volumetric capacity and intrinsic safety. However, the practical development of RMBs is hindered by the sluggish Mg2+ diffusion kinetics, including at the cathode-electrolyte interface (CEI) and within the cathode bulk. Herein, we propose an efficient strategy to manipulate the interfacial chemistry and coordination structure in oligolayered V2O5 (L-V2O5) for achieving rapid Mg2+ diffusion kinetics. In terms of the interfacial chemistry, the specific exposed crystal planes in L-V2O5 possess strong electron donating ability, which helps to promote the degradation dynamics of C-F/C-S bonds in the electrolyte, thereby establishing the inorganic-organic interlocking CEI layer for rapid Mg2+ diffusion. In terms of the coordination structure, the straightened V-O structure in L-V2O5 provides efficient ions diffusion path for accelerating Mg2+ diffusion in the cathode. As a result, the L-V2O5 delivers a high reversible capacity (355.3 mA h g-1 at 0.1 A g-1) and an excellent rate capability (161 mAh g-1 at 1 A g-1). Impressively, the interdigital micro-RMBs is firstly assembled, exhibiting excellent flexibility and practicability. This work gives deeper insights into the interface and interior ions diffusion for developing high-kinetics RMBs.

Unlocking a Fast Track for Magnesium Migration in Cu1.8S1-xSex via Anion-Tuning Chemistry.

Rechargeable magnesium batteries (rMBs) are promising candidates for next-generation batteries in which sulfides are widely used as cathode materials. The slow kinetics, low redox reversibility, and poor magnesium storage stability induced by the large Coulombic resistance and ionic polarization of Mg2+ ions have obstructed the development of high-performance rMBs. Herein, a Cu1.8S1-xSex cathode material with a two-dimensional sheet structure has been prepared by an anion-tuning strategy, achieving improved magnesium storage capacity and cycling stability. Element-specific synchrotron radiation analysis is evidence that selenium incorporation has indeed changed the chemical state of Cu species. Density functional theory calculations combined with kinetics analysis reveal that the anionic substitution endows the Cu1.8S1-xSex electrode with favorable charge-transfer kinetics and low ion diffusion barrier. The principal magnesium storage mechanisms and structural evolution process have been revealed in details based on a series of ex situ investigations. Our findings provide an effective heteroatom-tuning tactic of optimizing electrode structure toward advanced energy storage devices.

Batteries for electric vehicles: Technical advancements, environmental challenges, and market perspectives

AbstractThe rapid evolution of electric vehicles (EVs) highlights the critical role of battery technology in promoting sustainable transportation. This review offers a comprehensive introduction to the diverse landscape of batteries for EVs. In particular, it examines the impressive array of available battery technologies, focusing on the predominance of lithium‐based batteries, such as lithium‐ion and lithium‐metal variants. Additionally, it explores battery technologies beyond lithium (“post‐lithium”), including aluminum, sodium, and magnesium batteries. The potential of solid‐state batteries is also discussed, along with the current status of various battery types in EV applications. The review further addresses end‐of‐life treatment strategies for EV batteries, including reuse, remanufacturing, and recycling, which are essential for mitigating the environmental impact of batteries and ensuring sustainable lifecycle management. Finally, market perspectives and potential future research directions for battery technologies in EVs are also discussed.

Interfacial Coupling toward Bismuth Sulfide/MXene Heterostructures Empowering Reversible Magnesium Storage.

Bismuth-based compounds based on conversion-alloying reactions of multielectron transfer have attracted extensive attention as alternative anode candidates for rechargeable magnesium batteries (rMBs). However, the inadequate magnesium storage capability induced by the sluggish kinetics, poor reversibility, and terrible structural stability impedes their practical utilization. Herein, monodispersed Bi2S3 anchored on MXene has been prepared via a simple self-assembly strategy to induce the interfacial bonding of Ti-S and Ti-O-Bi. Unique superiority, including good electrical conductivity, high mechanical strength, and rapid charge transfer, is cleverly integrated together in the Bi2S3/MXene heterostructures, which endowed heterostructures with enhanced magnesium storage performance. Density functional theory calculations combined with kinetic behavior analyses confirm the favorable charge transfer and low ion diffusion barrier in hybrids. Furthermore, a stepwise insertion-conversion-alloying reaction mechanism is revealed in depth by ex situ investigations, which may also account for promoting performance. This work provides significant inspirations for constructing ingenious multicompositional hybrids by strong interfacial coupling engineering toward high-performance energy storage devices.