Search

Highlights A carbon free self supported Mott-Schottky heterostructure was constructed as an efficient cathode catalyst for lithium oxygen batteries, achieving homogeneous contact between the two materials for strong interfacial interactions. The heterostructure triggered interfacial perturbations and band structure changes, which accelerated oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics, resulting in an extremely long cycle life of 800 cycles and an extremely low overpotential of 0.73 V. Combined with advanced characterization techniques and density functional theory calculations, the underlying mechanism behind the boosted ORR/OER activities and the electrocatalytic mechanism were revealed.

Abstract Along with the constantly evolving functional microsystems toward more diversification, the more rigorous design deliberation of pursuing higher mass‐loading of electrode materials and low‐temperature fabrication compatibility have imposed unprecedented demand on integrable all‐solid‐state thin‐film microbatteries. While the classic thin‐film intercalation cathode prepared by vacuum‐based techniques inevitably encountered a post‐annealing process, tape‐casting technologies hold great merits both in terms of high‐mass loading and low‐temperature processing. In this work, a novel microbattery configuration is developed by the combination of traditional tape‐casting thick electrodes and sputtered inorganic thin‐film solid electrolytes (~3 μm lithium phosphorus oxynitride). Enabled by physically pressed or vapor‐deposited Li as an anode, solid‐state batteries with tape‐casted LiFePO4 electrodes exhibit outstanding cyclability and stability. To meet integration requirements, LiFePO4/LiPON/Si microbatteries were successfully fabricated at low temperatures and found to achieve a wide operating temperature range. This novel configuration has good prospects in promoting the thin‐film microbattery enabling a paradigm shift and satisfying diversified requirements.

Abstract A novel two‐stage profile maximum likelihood estimator is proposed to estimate the source location and the systematic errors jointly, with the aim of addressing the problem of source localisation using angle‐only measurements from a single sensor with unknown sensor altitude and systematic measurement errors. The proposed two‐stage profile maximum likelihood estimator algorithm is capable of decoupling the azimuth and elevation angle measurements while transforming the original maximum likelihood optimisation problem into two sub‐problems, that is, two‐dimensional‐projected maximum likelihood estimator and relative altitude maximum likelihood estimator. In terms of the two‐dimensional‐projected maximum likelihood estimator, an algorithm combining pseudo‐linear estimating and Kalman filtering is proposed to generate an initial estimate. Subsequently, a Gauss–Newton iterative method is developed to estimate the two‐dimensional‐projected target location and the azimuth systematic error jointly. The relative height maximum likelihood estimator is initialised using a pseudo‐linear estimator. Next, a Gauss–Newton iterative algorithm is adopted to estimate the elevation systematic error and the relative height. As indicated by the result of the simulation studies, the proposed algorithm exhibits an estimation performance close to the Cramér–Rao lower bound with unknown sensor altitude and systematic measurement errors.

Si-based anode materials have a relatively high theoretical specific capacity and low operating voltage, greatly enhancing the energy density of rechargeable lithium-ion batteries (LIBs). However, their practical application is seriously hindered by the instability of active particles and anode electrodes caused by the huge swelling during cycling. How to maintain the stability of the charge transfer network and interface structure of Si particles is full of challenges. To address this issue, we have developed a novel Si@Fe3O4/AC/CNR anode by in-situ growing one-dimensional high elastic carbon nano-ribbons to wrap Si nanoparticles. This special structure can construct fast channels of electron transport and lithium ion diffusion, and stabilize the surface structure of Si nanoparticles during cycling. With these promising architectural features, the Si@Fe3O4/AC/CNR composite possesses a high specific capacity of 1279.4 mAh/g at 0.5 A/g, and a superior cycling life with 80 % capacity retention after 700 cycles. Even at a high current density of 20.0 A/g, the composite still delivers a capacity of 621.2 mAh/g. The facile synthetic approach and high performance of Si@Fe3O4/AC/CNR anodes provide practical insight into advanced anode materials with large volume expansion for high-energy-density LIBs.

Solid polymer electrolytes (SPE) offer an outstanding choice because of their lightweight, flexibility, and excellent thin‐film forming ability. However, the low ionic conductivity and poor lithium ion transfer number (tLi+) restrict its application in all‐solid‐state lithium batteries (ASSLBs). Herein, UIO66‐X metal‐organic frameworks with controllable Lewis basicity, acidity, or neutrality functional groups are synthesized successfully and then incorporated into the poly (ethylene oxide) (PEO) matrix to fabricate SPE. The influence of different organic ligands on the interface interaction between PEO and LiTFSI is investigated by solid‐state nuclear magnetic resonance, Fourier transform infrared spectoscopy and Raman tests, as well as density functional theory calculations. The Lewis acidity group plays a key role in enhancing the ionic conductivity and tLi+. As a result, the constructed Li–Li symmetrical cells retain stable cycling for 2300 h and the LiFePO4‐based ASSLBs deliver outstanding electrochemical properties with 147 mAh g−1 of reversible capacity after 500 cycles at 1C and 60 °C, 131 mAh g−1 after 150 cycles at 0.1C and 30 °C. The fabricated SPEs are self‐standing and flexible with good mechanical stability, demonstrating the great potential for practical application. The results can guide choosing the inorganic filler to prepare high‐performance SPE.

Abstract Vanadium nitride (VN) electrode displays high‐rate, pseudocapacitive responses in aqueous electrolytes, however, it remains largely unclear in nonaqueous, Na+‐based electrolytes. The traditional view supposes a conversion‐type mechanism for Na+ storage in VN anodes but does not explain the phenomena of their size‐dependent specific capacities and underlying causes of pseudocapacitive charge storage behaviors. Herein, we insightfully reveal the VN anode exhibits a surface‐redox pseudocapacitive mechanism in nonaqueous, Na+‐based electrolytes, as demonstrated by kinetics analysis, experimental observations, and first‐principles calculations. Through ex situ X‐ray photoelectron spectroscopy and semiquantitative analyses, the Na+ storage is characterized by redox reactions occurring with the V5+/V4+ to V3+ at the surface of VN particles, which is different from the well‐known conversion reaction mechanism. The pseudocapacitive performance is enhanced through nanoarchitecture design via oxidized vanadium states at the surface. The optimized VN‐10 nm anode delivers a sodium‐ion storage capability of 106 mAh g−1 at the high specific current of 20 A g−1, and excellent cycling performance of 5000 cycles with negligible capacity losses. This work demonstrates the emerging opportunities of utilizing pseudocapacitive charge storage for realizing high‐rate sodium‐ion storage applications.

Abstract Surface‐redox pseudocapacitive nanomaterials show promise for fast‐charging energy storage. However, their high surface area usually leads to low density, which is not conducive to achieving both high volumetric capacity and high‐rate capability. Herein, we demonstrate that TiO2 nanosheets (meso‐TiO2‐NSs) with densely packed mesoporous are capable of fast pseudocapacitance‐dominated sodium‐ion storage, as well as high volumetric and gravimetric capacities. Through compressing treatment, the compaction density of meso‐TiO2‐NSs is up to ~1.6 g/cm3, combined with high surface area and high porosity with mesopore channels for rapid Na+ diffusion. The compacted meso‐TiO2‐NSs electrodes achieve high pseudocapacitance (93.6% of total charge at 1 mV/s), high‐rate capability (up to 10 A/g), and long‐term cycling stability (10,000 cycles). More importantly, the space‐efficiently packed structure enables high volumetric capacity. The thick‐film meso‐TiO2‐NSs anode with the mass loading of 10 mg/cm2 delivers a gravimetric capacity of 165 mAh/g and a volumetric capacity of 223 mAh/cm3 at 5 mA/cm2, much higher than those of commercial hard carbon anode (80 mAh/g and 86 mAh/cm3). This work highlights a pathway for designing a dense nanostructure that enables fast charge kinetics for high‐density sodium‐ion storage.

Pseudocapacitive materials with surface‐redox reactions are capable of realizing high capacities at ultrahigh rates; however, it remains a challenge in the synthesis of active components with high surface area to boost surface‐redox sodiation but restrain side reactions. Herein, a two‐step, topochemical synthesis of 2D mesoporous TiN (2D‐meso‐TiN) with high surface area and rich mesoporosities is presented. It is demonstrated that the sodium‐ion storage mechanism of TiN anode is based on the existence of surficial titanium oxides via redox reactions between Ti4+ and Ti3+. The interconnected, highly conductive 2D‐meso‐TiN with high surface area largely increases the pseudocapacitive capacities, leading to a high capacity of 160/93 mAh g−1 at 0.1/10 A g−1, which is much higher than 2D‐TiN (120/72 mAh g−1) and commercial TiN nanoparticles (57/30 mAh g−1). The surface‐redox (de)sodiation undergoes no destruction of crystalline TiN, which enables high initial coulombic efficiency and long‐term cycles. Furthermore, a novel hybrid sodium‐ion capacitor consisting of 2D‐meso‐TiN anode and Na3V2(PO4)3 cathode is assembled without any presodiation treatments. The hybrid capacitor delivers both high energy density (94 Wh kg−1 at 64 W kg−1) and high power density (38 Wh kg−1 at 4.4 kW kg−1), as well as long cycling stability.

Highlights A bi-service host with lithiophilic/sulfiphilic Fe2CoSe4 quantum dots embedded in three-dimensional ordered nitrogen-doped carbon skeleton is elaborately developed for both the sulfur cathode and Li anode synchronously. The highly dispersed Fe2CoSe4 quantum dots can not only act as a redox accelerator to promote the bidirectional conversion of LiPSs but also regulate the uniform Li plating/stripping to mitigate the growth of Li dendrite. The assembled Li-S full batteries achieve excellent long-term cyclability and a remarkable areal capacity of 8.41 mAh cm2 at high sulfur loading of 8.50 mg cm2, and the pouch full battery also displays high capacity and cycling-stability at lean electrolyte condition.

Sodium ion storage remains relatively unexplored in comparison with well-understood lithium ion storage mechanisms. Here, the authors systematically investigate the surface-redox sodium ion storage properties of anatase titanium dioxide, which delivers excellent rate capability, cycling stability and low overpotentials.

The development of cathode materials with high specific capacity is the key to obtaining high-performance lithium-ion batteries, which are crucial for the efficient utilization of clean energy and the realization of carbon neutralization goals. Li-rich Mn-based cathode materials (LRM) exhibit high specific capacity because of both cationic and anionic redox activity and are expected to be developed and applied as cathode materials for a new generation of high-energy density lithium-ion batteries. Nevertheless, the difficulty of regulating anionic redox reactions poses significant challenges to LRM, such as low initial Coulombic efficiency, poor rate capability, and fast cycling capacity and voltage decay. To address the existing challenges of LRM, this review introduces their basic physicochemical characteristics in detail, analyzes the original causes of these challenges, focuses on the recent progress of the modification strategies, and then especially discusses the development prospects of LRM from different aspects.

Abstract There are plenty of issues need to be solved before the practical application of Li- and Mn-rich cathodes, including the detrimental voltage decay and mediocre rate capability, etc. Element doping can effectively solve the above problems, but cause the loss of capacity. The introduction of appropriate defects can compensate the capacity loss; however, it will lead to structural mismatch and stress accumulation. Herein, a three-in-one method that combines cation–polyanion co-doping, defect construction, and stress engineering is proposed. The co-doped Na+/SO4 2− can stabilize the layer framework and enhance the capacity and voltage stability. The induced defects would activate more reaction sites and promote the electrochemical performance. Meanwhile, the unique alternately distributed defect bands and crystal bands structure can alleviate the stress accumulation caused by changes of cell parameters upon cycling. Consequently, the modified sample retains a capacity of 273 mAh g−1 with a high-capacity retention of 94.1% after 100 cycles at 0.2 C, and 152 mAh g−1 after 1000 cycles at 2 C, the corresponding voltage attenuation is less than 0.907 mV per cycle.

Abstract With its high theoretical capacity, lithium (Li) metal is recognized as the most potential anode for realizing a high‐performance energy storage system. A series of questions (severe safety hazard, low Coulombic efficiency, short lifetime, etc.) induced by uncontrollable dendrites growth, unstable solid electrolyte interface layer, and large volume change, make practical application of Li‐metal anodes still a threshold. Due to their highly appealing properties, carbon‐based materials as hosts to composite with Li metal have been passionately investigated for improving the performance of Li‐metal batteries. This review displays an overview of the critical role of carbon‐based hosts for improving the comprehensive performance of Li‐metal anodes. Based on correlated mainstream models, the main failure mechanism of Li‐metal anodes is introduced. The advantages and strategies of carbon‐based hosts to address the corresponding challenges are generalized. The unique function, existing limitation, and recent research progress of key carbon‐based host materials for Li‐metal anodes are reviewed. Finally, a conclusion and an outlook for future research of carbon‐based hosts are presented. This review is dedicated to summarizing the advances of carbon‐based materials hosts in recent years and providing a reference for the further development of carbon‐based hosts for advanced Li‐metal anodes.

Abstract The large overpotential and poor cycle stability caused by inactive redox reactions are tough challenges for lithium–oxygen batteries (LOBs). Here, a composite microsphere material comprising NiCo2O4@CeO2 is synthesized via a hydrothermal approach followed by an annealing processing, which is acted as a high performance electrocatalyst for LOBs. The unique microstructured catalyst can provide enough catalytic surface to facilitate the barrier‐free transport of oxygen as well as lithium ions. In addition, the special microsphere and porous nanoneedles structure can effectively accelerate electrolyte penetration and the reversible formation and decomposition process of Li2O2, while the introduction of CeO2 can increase oxygen vacancies and optimize the electronic structure of NiCo2O4, thereby enhancing the electron transport of the whole electrode. This kind of catalytic cathode material can effectively reduce the overpotential to only 1.07 V with remarkable cycling stability of 400 loops under 500 mA g−1. Based on the density functional theory calculations, the origin of the enhanced electrochemical performance of NiCo2O4@CeO2 is clarified from the perspective of electronic structure and reaction kinetics. This work demonstrates the high efficiency of NiCo2O4@CeO2 as an electrocatalyst and confirms the contribution of the current design concept to the development of LOBs cathode materials.

Abstract Lithium–sulfur (Li–S) batteries are regarded as the most promising next‐generation energy storage systems due to their high energy density and cost‐effectiveness. However, their practical applications are seriously hindered by several inevitable drawbacks, especially the shuttle effects of soluble lithium polysulfides (LiPSs) which lead to rapid capacity decay and short cycling lifespan. This review specifically concentrates on the shuttle path of LiPSs and their interaction with the corresponding cell components along the moving way, systematically retrospect the recent advances and strategies toward polysulfides diffusion suppression. Overall, the strategies for the shuttle effect inhibition can be classified into four parts, including capturing the LiPSs in the sulfur cathode, reducing the dissolution in electrolytes, blocking the shuttle channels by functional separators, and preventing the chemical reaction between LiPSs and Li metal anode. Herein, the fundamental aspect of Li–S batteries is introduced first to give an in‐deep understanding of the generation and shuttle effect of LiPSs. Then, the corresponding strategies toward LiPSs shuttle inhibition along the diffusion path are discussed step by step. Finally, general conclusions and perspectives for future research on shuttle issues and practical application of Li–S batteries are proposed.

Abstract High-performance and low-cost sodium-ion capacitors (SICs) show tremendous potential applications in public transport and grid energy storage. However, conventional SICs are limited by the low specific capacity, poor rate capability, and low initial coulombic efficiency (ICE) of anode materials. Herein, we report layered iron vanadate (Fe5V15O39 (OH)9·9H2O) ultrathin nanosheets with a thickness of ~ 2.2 nm (FeVO UNSs) as a novel anode for rapid and reversible sodium-ion storage. According to in situ synchrotron X-ray diffractions and electrochemical analysis, the storage mechanism of FeVO UNSs anode is Na+ intercalation pseudocapacitance under a safe potential window. The FeVO UNSs anode delivers high ICE (93.86%), high reversible capacity (292 mAh g−1), excellent cycling stability, and remarkable rate capability. Furthermore, a pseudocapacitor–battery hybrid SIC (PBH-SIC) consisting of pseudocapacitor-type FeVO UNSs anode and battery-type Na3(VO)2(PO4)2F cathode is assembled with the elimination of presodiation treatments. The PBH-SIC involves faradaic reaction on both cathode and anode materials, delivering a high energy density of 126 Wh kg−1 at 91 W kg−1, a high power density of 7.6 kW kg−1 with an energy density of 43 Wh kg−1, and 9000 stable cycles. The tunable vanadate materials with high-performance Na+ intercalation pseudocapacitance provide a direction for developing next-generation high-energy capacitors.

Abstract Combining MoSe2 with other transition metal dichalcogenides to form a hybrid nanostructure is an effective route to enhance the electrocatalytic activities for hydrogen evolution reaction (HER). In this study, MoSe2-Ni3Se4 hybrid nanoelectrocatalysts with a flower-like morphology are synthesized by a seed-induced solution approach. Instead of independently nucleating to form separate nanocrystals, the Ni3Se4 component tends to nucleate and grow on the surfaces of ultrathin nanoflakes of MoSe2 to form a hybrid nanostructure. MoSe2–Ni3Se4 hybrid nanoelectrocatalysts with different Mo:Ni ratios are prepared and their HER catalytic activities are compared. The results show that the HER activities are affected by the Mo:Ni ratios. In comparison with pure MoSe2, the MoSe2-Ni3Se4 hybrid nanoelectrocatalysts having a Mo:Ni molar ratio of 2:1 exhibit enhanced HER properties with an overpotential of 203 mV at 10 mA/cm2 and a Tafel slope of 57 mV per decade. Improved conductivity and increased turnover frequencies (TOFs) are also observed for the MoSe2-Ni3Se4 hybrid samples.

Lithium cobalt oxide (LCO) cathode has been widely applied in 3C products (computer, communication, and consumer), and LCO films are currently the most promising cathode materials for thin-film lithium batteries (TFBs) due to their high volumetric energy density and favorable durability. Most LCO thin films are fabricated by physical vapor deposition (PVD) techniques, while the influence of preparation on the materials’ properties and electrochemical performance has not been highlighted. In this review, the dominant effects (heating, substrate, power, atmosphere, etc.) on LCO thin films are summarized, and the LCO thin films fabricated by other techniques (spin coating, sol–gel, atomic layer deposition, pulsed laser deposition, etc.) are outlined. Moreover, the modification strategies including bulk doping and surface coating for powder and thin-film LCO electrodes are discussed in detail. This review may pave the way for developing novel, durable, and high-performance LCO thin films by versatile methods for TFB and other energy storage devices.

Abstract The two major limitations in the application of SnO2 for lithium-ion battery (LIB) anodes are the large volume variations of SnO2 during repeated lithiation/delithiation processes and a large irreversible capacity loss during the first cycle, which can lead to a rapid capacity fade and unsatisfactory initial Coulombic efficiency (ICE). To overcome these limitations, we developed composites of ultrafine SnO2 nanoparticles and in situ formed Co(CoSn) nanocrystals embedded in an N-doped carbon matrix using a Co-based metal–organic framework (ZIF-67). The formed Co additives and structural advantages of the carbon-confined SnO2/Co nanocomposite effectively inhibited Sn coarsening in the lithiated SnO2 and mitigated its structural degradation while facilitating fast electronic transport and facile ionic diffusion. As a result, the electrodes demonstrated high ICE (82.2%), outstanding rate capability (~ 800 mAh g−1 at a high current density of 5 A g−1), and long-term cycling stability (~ 760 mAh g−1 after 400 cycles at a current density of 0.5 A g−1). This study will be helpful in developing high-performance Si (Sn)-based oxide, Sn/Sb-based sulfide, or selenide electrodes for LIBs. In addition, some metal organic frameworks similar to ZIF-67 can also be used as composite templates.

Robust techniques critically improve bearing-only target localization when the relevant measurements are being corrupted by impulsive noise. Resistance to isolated gross errors refers to the conventional least absolute residual (LAR) method, and its estimate can be determined by linear programming when pseudolinear equations are set. The LAR approach, however, cannot reduce the bias attributed to the correlation between system matrices and noise vectors. In the present study, perturbations are introduced into the elements of the system matrix and the data vector simultaneously, and the total optimization problem is formulated based on least absolute deviations. Subsequently, an equivalent form of total least absolute residuals (TLAR) is obtained, and an algorithm is developed to calculate the robust estimate by dual ascent algorithms. Moreover, the performance of the proposed method is verified through the numerical simulations by using two types of localization geometries, i.e., random and linear. As revealed from the results, the TLAR algorithm is capable of exhibiting significantly higher localization accuracy as compared with the LAR method.

Lithium cobalt oxide (LCO) is the most widely used cathode materials in electronic devices due to the high working potential and dense tap density, but the performance is limited by the unstable interfaces at high potential. Herein, LiF thin film is sputtered on the surface of LCO electrodes for enhancing the electrochemical performance and reducing the voltage polarization. The polarization components are discussed and quantified by analyzing the relationship between electrochemical polarization and charger transfer resistance, as well as that between concentration polarization and Li-ion diffusion coefficients. In addition, the decreased charge transfer resistance, increased lithium-ion diffusion coefficients, and stabilized crystal structure of LiF-coated LCO are confirmed by various electrochemical tests and in-situ XRD experiments. Compared to that of pristine LCO, the capacity and cycling performance of LiF-coated LCO is improved, and the overpotential is reduced upon cycling. This work provides reference for quantifying the various polarization components, and the strategy of coating LiF film could be applied in developing other analogous cathode materials.

Abstract The corrosion of Li‐ and Mn‐rich (LMR) electrode materials occurring at the solid–liquid interface will lead to extra electrolyte consumption and transition metal ions dissolution, causing rapid voltage decay, capacity fading, and detrimental structure transformation. Herein, a novel strategy is introduced to suppress this corrosion by designing an Na+‐doped LMR (Li1.2Ni0.13Co0.13Mn0.54O2) with abundant stacking faults, using sodium dodecyl sulfate as surfactant to ensure the uniform distribution of Na+ in deep grain lattices—not just surface‐gathering or partially coated. The defective structure and deep distribution of Na+ are verified by Raman spectrum and high‐resolution transmission electron microscopy of the as‐prepared electrodes before and after 200 cycles. As a result, the modified LMR material shows a high reversible discharge specific capacity of 221.5 mAh g−1 at 0.5C rate (1C = 200 mA g−1) after 200 cycles, and the capacity retention is as high as 93.1% which is better than that of pristine‐LMR (64.8%). This design of Na+ is uniformly doped and the resultanting induced defective structure provides an effective strategy to enhance electrochemical performance which should be extended to prepare other advanced cathodes for high performance lithium‐ion batteries.

A constrained least-squares (CLS) 3D source localization method is presented for acoustic sensor networks with sensor position errors. The proposed approach uses angles of arrivals (AOAs) and gain ratios of arrival (GROAs) measured simultaneously at each node to estimate the source position jointly. Compared to AOA-only localization methods, the GROAs can be used in conjunction with AOA measurements so as to get more accurate results by exploiting the geometrical relationship between these two measurements. Compared to time difference of arrival localization methods, the proposed algorithm does not require accurate time synchronization over different nodes. The theoretical mean-square error matrices of the proposed approach are derived and they are exactly equal to the Cramér–Rao bound for Gaussian noise under the small error condition. Simulations validate the performance of the proposed estimator.

Compared to the well-investigated Li+ intercalation into layered TiO2(B), the Na+ storage properties of TiO2(B) remain relatively unexplored. Herein, an insight into the Na+ storage mechanism of TiO2(B) is gained by simultaneously investigating the structural evolution and reaction kinetics of the nanosheets (NSs) and nanowires (NWs) with different specific surface areas. Based on ex situ characterizations, the Na+ (de)intercalation into layered TiO2(B) follows a solid-solution reaction with negligible lattice changes. Detailed kinetic analysis reveals the intercalation pseudocapacitance of sodium-ion storage in TiO2(B), with a high capacitive contribution of ∼90% for both the NSs and NWs electrodes. The Na+ storage capacities and capacitive dominant responses of TiO2(B) anodes are independent of their specific surface area and morphology, demonstrating the intrinsic intercalation pseudocapacitance of sodium-ion storage in TiO2(B). Density functional theory (DFT) calculations reveal different storage sites in TiO2(B) for the accommodation of Na+ and Li+ ions, leading to the lower Na+ storage capacity of 120 mA h g−1 than that of Li+ storage. Due to the advantages of intercalation pseudocapacitance, the TiO2(B) anode displays excellent high-rate capability and long-term cycling stability for Na+ storage. [ABSTRACT FROM AUTHOR]

High electrochemical reversibility is required for the application of high-energy- density lithium (Li) metal batteries; however, inactive Li formation and SEI (solid electrolyte interface)-instability- induced electrolyte consumption cause low Coulombic efficiency (CE). The prior interfacial chemical designs in terms of alloying kinetics have been used to enhance the CE of Li metal anode; however, the role of its redox chemistry at heterointerfaces remains a mystery. Herein, the relationship between heterointerfacial redox chemistry and electrochemical transformation reversibility is investigated. It is demonstrated that the lower redox potential at heterointerface contributes to higher CE, and this enhancement in CE is primarily due to the regulation of redox chemistry to Li deposition behavior rather than the formation of SEI films. Low oxidation potential facilitates the formation of the surface with the highly electrochemical binding feature after Li stripping, and low reduction potential can maintain binding ability well during subsequent Li plating, both of which homogenize Li deposition and thus optimize CE. In particular, Mg hetero-metal with ultra-low redox potential enables Li metal anode with significantly improved CE (99.6%) and stable cycle life for 700 cycles at 3.0 mA cm-2. This work provides insight into the heterointerfacial design principle of next-generation negative electrodes for highly reversible metal batteries. [ABSTRACT FROM AUTHOR]