An autotransferable alloy overlayer toward stable sodium metal anodes.

Sodium (Na) metal anodes receive significant attention due to their high theoretical specific energy and cost-effectiveness. However, the high reactivity of Na foil anodes and the irregular surfaces have posed challenges to the operability and reliability of Na metals in battery applications. In the absence of inert environmental protection conditions, constructing a uniform, dense, and sodiophilic Na metal anode surface is crucial for homogenizing Na deposition, but remains less-explored. Herein, we fabricated a Tin (Sn) nanoparticle-assembled film conforming to separator pores, which provided ample space for accommodating volumetric expansion during the Na alloying process. Subsequently, a seamless Na-Sn alloy overlayer was formed and transferred onto the Na foil during Na plating through a separator-assisted technique, thereby overcoming conventional operational limitations of metallic Na. As compared to traditional volumetrically expanded cracked ones, the present autotransferable, highly sodiophilic, ion-conductive, and seamless Na-Sn alloy overlayer serves as uniform nucleation sites, thereby reducing nucleation and diffusion barriers and facilitating the compact deposition of metallic Na. Consequently, the autotransferable alloy layer enables a high average Coulombic efficiency of 99.9 % at 3.0 mA cm-2 and 3.0 mAh cm-2 in the half cells as well as minimal polarization overpotentials in symmetric cells, both during prolonged cycling 1200 h. Furthermore, the assembled Na||Sn-1.0h-PP||Na3V2(PO4)3@C@CNTs full cell delivers high capacity retention of 97.5 % after 200 cycles at a high cathodic mass loading.

Tailoring Li Deposition by Regulating Structural Connectivity of Electrochemical Li Reservoir in Li-metal Batteries.

Irregular Li deposition is the major reason for poor reversibility and cycle instability in Li metal batteries, even leading to safety hazards, the causes of which have been extensively explored. The structural disconnection induced by completely dissolving Li in the traditional testing protocol is a key factor accounting for irregular Li growth during the subsequent deposition process. Herein, the critical role played by the structural connectivity of electrochemical Li reservoir in subsequent Li deposition behaviors is elucidated and a morphology-performance correlation is established. The structural connection and resultant well-distributed morphology of the in situ electrochemical Li reservoir ensure efficient electron transfer and Li+ diffusion pathway, finally leading to homogenized Li nucleation and growth. Tailoring the geometry of Li reservoir can improve the coulombic efficiency and cyclability of anode-free Li metal batteries by optimizing Li deposition behavior.

Design principles of heterointerfacial redox chemistry for highly reversible lithium metal anode.

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.

Artificial Post-Cycled Structure Modulation Towards Highly Stable Li-Rich Layered Cathode.

High-capacity Li-rich layered oxides (LLOs) suffer from severe structure degradation due to the utilization of hybrid anion- and cation-redox activity. The native post-cycled structure, composed of progressively densified defective spinel layer (DSL) and intrinsic cations mixing, is deemed as the hindrance of the rapid and reversible de/intercalation of Li+ . Herein, the artificial post-cycled structure consisting of artificial DSL and inner cations mixing is in situ constructed, which would act as a shield against the irreversible oxygen emission and undesirable transition metal migration by suppressing anion redox activity and modulating cation mixing. Eventually, the modified DSL-2% Li-rich cathode demonstrates remarkable electrochemical properties with a high discharge capacity of 187 mAh g-1 after 500 cycles at 2 C, and improved voltage stability. Even under harsh operating conditions of 50 °C, DSL-2% can provide a high discharge capacity of 168 mAh g-1 after 250 cycles at 2 C, which is much higher than that of pristine LLO (92 mAh g-1 ). Furthermore, the artificial post-cycled structure provides a novel perspective on the role of native post-cycled structure in sustaining the lattice structure of the lithium-depleted region and also provides an insightful universal design principle for highly stable intercalated materials with anionic redox activity.

Role of Substitution Elements in Enhancing the Structural Stability of Li-Rich Layered Cathodes.

Element doping/substitution has been recognized as an effective strategy to enhance the structural stability of layered cathodes. However, abundant substitution studies not only lack a clear identification of the substitution sites in the material lattice, but the rigid interpretation of the transition metal (TM)-O covalent theory is also not sufficiently convincing, resulting in the doping/substitution proposals being dragged into design blindness. In this work, taking Li1.2Ni0.2Mn0.6O2 as a prototype, the intense correlation between the "disordered degree" (Li/Ni mixing) and interface-structure stability (e.g., TM-O environment, slab/lattice, and Li+ reversibility) is revealed. Specifically, the degree of disorder induced by the Mg/Ti substitution extends in the opposite direction, conducive to sharp differences in the stability of TM-O, Li+ diffusion, and anion redox reversibility, delivering fairly distinct electrochemical performance. Based on the established paradigm of systematic characterization/analysis, the "degree of disorder" has been shown to be a powerful indicator of material modification by element substitution/doping.

Dual-Functional Lithiophilic/Sulfiphilic Binary-Metal Selenide Quantum Dots Toward High-Performance Li-S Full Batteries.

The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides (LiPSs) shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode. Herein, a bi-service host with Co-Fe binary-metal selenide quantum dots embedded in three-dimensional inverse opal structured nitrogen-doped carbon skeleton (3DIO FCSe-QDs@NC) is elaborately designed for both sulfur cathode and Li metal anode. The highly dispersed FCSe-QDs with superb adsorptive-catalytic properties can effectively immobilize the soluble LiPSs and improve diffusion-conversion kinetics to mitigate the polysulfide-shutting behaviors. Simultaneously, the 3D-ordered porous networks integrated with abundant lithophilic sites can accomplish uniform Li deposition and homogeneous Li-ion flux for suppressing the growth of dendrites. Taking advantage of these merits, the assembled Li-S full batteries with 3DIO FCSe-QDs@NC host exhibit excellent rate performance and stable cycling ability (a low decay rate of 0.014% over 2,000 cycles at 2C). Remarkably, a promising areal capacity of 8.41 mAh cm-2 can be achieved at the sulfur loading up to 8.50 mg cm-2 with an ultra-low electrolyte/sulfur ratio of 4.1 µL mg-1. This work paves the bi-serve host design from systematic experimental and theoretical analysis, which provides a viable avenue to solve the challenges of both sulfur and Li electrodes for practical Li-S full batteries.

Regulation of Interfacial Lattice Oxygen Activity by Full-Surface Modification Engineering towards Long Cycling Stability for Co-Free Li-Rich Mn-Based Cathode.

The construction of a protective layer for stabilizing anion redox reaction is the key to obtaining long cycling stability for Li-rich Mn-based cathode materials. However, the protection of the exposed surface/interface of the primary particles inside the secondary particles is usually ignored and difficult, let alone the investigation of the impact of the surface engineering of the internal primary particles on the cycling stability. In this work, an efficient method to regulate cycling stability is proposed by simply adjusting the distribution state of the boron nickel complexes coating layer. Theoretical calculation and experimental results display that the full-surface boron nickel complexes coating layer can not only passivate the activity of interface oxygen and improve its stability but also play the role of sharing voltage and protective layer to gradually activate the oxygen redox reaction during cycling. As a result, the elaborately designed cobalt-free Li-rich Mn-based cathode displays the highest discharge-specific capacity retentions of 91.1% after 400 cycles at 1 C and 94.3% even after 800 cycles at 5 C. In particular, the regulation strategy has well universality and is suitable for other high-capacity Li-rich cathode materials.

Stainless Steel-Like Passivation Inspires Persistent Silicon Anodes for Lithium-Ion Batteries.

Passivation of stainless steel by additives forming mass-transport blocking layers is widely practiced, where Cr element is added into bulk Fe-C forming the Cr2 O3 -rich protective layer. Here we extend the long-practiced passivation concept to Si anodes for lithium-ion batteries, incorporating the passivator of LiF/Li2 CO3 into bulk Si. The passivation mechanism is studied by various ex situ characterizations, redox peak contour maps, thickness evolution tests, and finite element simulations. The results demonstrate that the passivation can enhance the (de)lithiation of Li-Si alloys, induce the formation of F-rich solid electrolyte interphase, stabilize the Si/LiF/Li2 CO3 composite, and mitigate the volume change of Si anodes upon cycling. The 3D passivated Si anode can fully retain a high capacity of 3701 mAh g-1 after 1500 cycles and tolerate high rates up to 50C. This work provides insight into how to construct durable Si anodes through effective passivation.

Adjustable Mixed Conductive Interphase for Dendrite-Free Lithium Metal Batteries.

Lithium (Li) metal batteries with high energy density are of great promise for next-generation energy storage; however, they suffer from severe Li dendritic growth and an unstable solid electrolyte interphase. In this study, a mixed ionic and electronic conductive (MIEC) interphase layer with an adjustable ratio assembled by ZnO and Zn nanoparticles is developed. During the initial cycle, the in situ formed Li2O with high ionic conductivity and a lithiophilic LiZn alloy with high electronic conductivity enable fast Li+ transportation in the interlayer and charge transfer at the ion/electron conductive junction, respectively. The optimized interface kinetics is achieved by balancing the ion migration and charge transfer in the MIEC Li2O-LiZn interphase. As a result, the symmetric cell with MIEC interphase delivers superior cycling stability of over 1200 h. Also, Li||Zn-ZnO@PP||LFP (LFP = LiFePO4) full cells exhibit long cyclic life for 2000 cycles with a very high capacity retention of 91.5% at a high rate of 5 C and stable cycling for 350 cycles at a high LFP loading mass of 13.27 mg cm-2.

In Situ Induced Lattice-Matched Interfacial Oxygen-Passivation-Layer Endowing Li-Rich and Mn-Based Cathodes with Ultralong Life.

The high capacity of Li-rich and Mn-based (LRM) cathode materials is originally due to the unique hybrid anion- and cation redox, which also induces detrimental oxygen escape. Furthermore, the counter diffusion of released oxygen (into electrolyte) and induced oxygen vacancies (into the interior bulk phase) that occurs at the interface will cause uncontrolled phase collapse and other issues. Therefore, due to its higher working voltage (>4.7 V) than the activation voltage of lattice oxygen in LRM (≈4.5 V), the anion-redox-free and structurally consistent cobalt-free LiNi0.5 Mn1.5 O4 (LNMO) is selected to in situ construct a robust, crystal-dense and lattice-matched oxygen-passivation-layer (OPL) on the surface of LRM particles by the electrochemical delithiation to protect the core layered components. As expected, the modified sample displays continuously decreasing interfacial impedance and high specific capacity of 135.5 mAh g-1 with a very small voltage decay of 0.67 mV per cycle after 1000 cycles at 2 C rate. Moreover, the stress accumulation during cycling is mitigated effectively. This semicoherent OPL strengthens the surface stability and interrupts the counter diffusion of oxygen and oxygen vacancies in LRM cathode materials, which would provide guidance for designing high-energy-density layered cathode materials.

Recent Advances and Strategies toward Polysulfides Shuttle Inhibition for High-Performance Li-S Batteries.

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.

Challenge and Strategies in Room Temperature Sodium-Sulfur Batteries: A Comparison with Lithium-Sulfur Batteries.

Metal-sulfur batteries exhibit great potential as next-generation rechargeable batteries due to the low sulfur cost and high theoretical energy density. Sodium-sulfur (Na-S) batteries present higher feasibility of long-term development than lithium-sulfur (Li-S) batteries in technoeconomic and geopolitical terms. Both lithium and sodium are alkali metal elements with body-centered cubic structures, leading to similar physical and chemical properties and exposing similar issues when employed as the anode in metal-sulfur batteries. Indeed, some inspiration for mechanism researches and strategies in Na-S systems comes from the more mature Li-S systems. However, the dissimilarities in microscopic characteristics determine that Na-S is not a direct Li-S analogue. Herein, the daunting challenges derived by the differences of fundamental characteristics in Na-S and Li-S systems are discussed. And the corresponding strategies in Na-S batteries are reviewed. Finally, general conclusions and perspectives toward the research direction are presented based on the dissimilarities between both systems. This review attempts to provide important insights to facilitate the assimilation of the available knowledge on Li-S systems for accelerating the development of Na-S batteries on the basis of their dissimilarities.

Sputtering Coating of Lithium Fluoride Film on Lithium Cobalt Oxide Electrodes for Reducing the Polarization of Lithium-Ion Batteries.

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.

Boosting the Electrochemical Performance of Li- and Mn-Rich Cathodes by a Three-in-One Strategy.

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+/SO42- 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.

A Universal Strategy toward the Precise Regulation of Initial Coulombic Efficiency of Li-Rich Mn-Based Cathode Materials.

Li-rich Mn-based cathode materials (LRMs) are potential cathode materials for high energy density lithium-ion batteries. However, low initial Coulombic efficiency (ICE) severely hinders the commercialization of LRM. Herein, a facile oleic acid-assisted interface engineering is put forward to precisely control the ICE, enhance reversible capacity and rate performance of LRM effectively. As a result, the ICE of LRM can be precisely adjusted from 84.1% to 100.7%, and a very high specific capacity of 330 mAh g-1 at 0.1 C, as well as outstanding rate capability with a fascinating specific capacity of 250 mAh g-1 at 5 C, are harvested. Theoretical calculations reveal that the introduced cation/anion double defects can reduce the diffusion barrier of Li+ ions, and in situ surface reconstruction layer can induce a self-built-in electric field to stabilize the surface lattice oxygen. Moreover, this facile interface engineering is universal and can enhance the ICEs of other kinds of LRM effectively. This work provides a valuable new idea for improving the comprehensive electrochemical performance of LRM through multistrategy collaborative interface engineering technology.

Challenges and Recent Advances in High Capacity Li-Rich Cathode Materials for High Energy Density Lithium-Ion Batteries.

Li-rich cathode materials have attracted increasing attention because of their high reversible discharge capacity (>250 mA h g-1 ), which originates from transition metal (TM) ion redox reactions and unconventional oxygen anion redox reactions. However, many issues need to be addressed before their practical applications, such as their low kinetic properties and inefficient voltage fading. The development of cutting-edge technologies has led to cognitive advances in theory and offer potential solutions to these problems. Herein, a recent in-depth understanding of the mechanisms and the frontier electrochemical research progress of Li-rich cathodes are reviewed. In addition, recent advances associated with various strategies to promote the performance and the development of modification methods are discussed. In particular, excluding Li-rich Mn-based (LRM) cathodes, other branches of the Li-rich cathode materials are also summarized. The consistent pursuit is to obtain energy storage devices with high capacity, reliable practicability, and absolute safety. The recent literature and ongoing efforts in this area are also described, which will create more opportunities and new ideas for the future development of Li-rich cathode materials.

Phosphorus-Doped Metal-Organic Framework-Derived CoS2 Nanoboxes with Improved Adsorption-Catalysis Effect for Li-S Batteries.

Lithium-sulfur (Li-S) batteries are regarded as one of the most promising next-generation battery technologies owing to their ultrahigh energy density up to 2600 W h kg-1 and low cost. However, major challenges still remain in the application of Li-S batteries, such as shuttle effect and sluggish redox kinetics. Herein, it is demonstrated that phosphorus doping can not only significantly improve the polysulfide adsorption but also enhance the catalysis effects of metal-organic framework-derived CoS2 nanoboxes in Li-S batteries. Consequently, a modified separator integrated with P-CoS2 and carbon nanotubes effectively suppresses the polysulfide shuttle and propels the redox kinetics of polysulfides, thus promising higher specific discharge capacity, better rate, and stable cycle performance. Even under the high sulfur loading condition (4.8 mg cm-2), the areal discharge capacity of the cell with the functional separator can still remain at 4.5 mA h cm-2 after 100 cycles at 0.2 C. More importantly, this work may encourage more effort on anion doping for engineering the polar surface of transition-metal compounds to further mediate the interfacial redox chemistry between transition-metal compounds and polysulfides in Li-S batteries.

Multiscale Deficiency Integration by Na-Rich Engineering for High-Stability Li-Rich Layered Oxide Cathodes.

Lithium-rich manganese-based (LRM) layered oxides are considered as one of the most promising cathode materials for next-generation high-energy-density lithium-ion batteries (LIBs) because of their high specific capacity (>250 mAh g-1). However, they also go through severe capacity decay, serious voltage fading, and poor rate capability during cycling. Herein, a multiscale deficiency integration, including surface coating, subsurface defect construction, and bulk doping, is realized in a Li1.2Mn0.54Ni0.13Co0.13O2 cathode material by facile Na-rich engineering through a sol-gel method. This multiscale design can significantly improve the bulk and surface structural stability and diffusion rate of Li+ ions of electrode materials. Specifically, an outstanding specific capacity of 201 mAh g-1 is delivered at 1C of the designed cathode material after 400 cycles, relating to a large capacity retention of 89.0%. Meanwhile, the average voltage is retained up to 3.13 V with a large voltage retention of 89.6% and the energy density is maintained at 627.4 Wh kg-1. In situ X-ray diffraction (XRD), ex situ transmission electron microscopy (TEM) investigations, and density functional theory (DFT) calculations are conducted to explain the greatly enhanced electrochemical properties of a LRM cathode. We believe that this strategy would be a meaningful reference of LRM cathode materials for the research in the future.

Li-Zn Overlayer to Facilitate Uniform Lithium Deposition for Lithium Metal Batteries.

The highly reactive nature and rough surface of Li foil can lead to the uncontrollable formation of Li dendrites when employed as an anode in a lithium metal battery. Thus, it could be of great practical utility to create uniform, electrochemically stable, and "lithiophilic" surfaces to realize homogeneous deposition of Li. Herein, a LiZn alloy layer is deposited on the surface of Li foil by e-beam evaporation. The idea is to introduce a uniform alloy surface to increase the active area and make use of the Zn sites to induce homogeneous nucleation of Li. The results show that the alloy film protected the Li metal anode, allowing for a longer cycling life with a lower deposition overpotential over a pure-Li metal anode in symmetric Li cells. Furthermore, full cells pairing the modified lithium anode with a LiFePO4 cathode showed an incremental increase in Coulombic efficiency compared with pure-Li. The concept of using only an alloy modifying layer by an in-situ e-beam deposition synthesis method offers a potential method for enabling lithium metal anodes for next-generation lithium batteries.

Function and Application of Defect Chemistry in High-Capacity Electrode Materials for Li-Based Batteries.

Current commercial Li-based batteries are approaching their energy density limitation, yet still cannot satisfy the energy density demand of the high-end devices. Hence, it is critical to developing advanced electrode materials with high specific capacity. However, these electrode materials are facing challenges of severe structural degradation and fast capacity fading. Among various strategies, constructing defects in electrode materials holds great promise in addressing these issues. Herein, we summarize a series of significant defect engineering in the high-capacity electrode materials for Li-based batteries. The detailed retrospective on defects specification, function mechanism, and corresponding application achievements on these electrodes are discussed from the view of point, line, planar, volume defects. Defect engineering can not only stabilize the structure and enhance electric/ionic conductivity, but also act as active sites to improve the ionic storage and bonding ability of electrode materials to Li metal. We hope this review can spark more perspectives on evaluating high-energy-density Li-based batteries.