High-Safety and High-Energy-Density Lithium Metal Batteries in a Novel Ionic-Liquid Electrolyte

Rechargeable lithium metal batteries are next generation energy storage devices with high energy density, but face challenges in achieving high energy density, high safety, and long cycle life. Here, lithium metal batteries in a novel nonflammable ionic-liquid (IL) electrolyte composed of 1-ethyl-3-methylimidazolium (EMIm) cations and high-concentration bis(fluorosulfonyl)imide (FSI) anions, with sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as a key additive are reported. The Na ion participates in the formation of hybrid passivation interphases and contributes to dendrite-free Li deposition and reversible cathode electrochemistry. The electrolyte of low viscosity allows practically useful cathode mass loading up to ≈16 mg cm⁻². Li anodes paired with lithium cobalt oxide (LiCoO₂) and lithium nickel cobalt manganese oxide (LiNi_0.8Co_0.1Mn_0.1O₂, NCM 811) cathodes exhibit 99.6–99.9% Coulombic efficiencies, high discharge voltages up to 4.4 V, high specific capacity and energy density up to ≈199 mAh g⁻¹ and ≈765 Wh kg⁻¹ respectively, with impressive cycling performances over up to 1200 cycles. Highly stable passivation interphases formed on both electrodes in the novel IL electrolyte are the key to highly reversible lithium metal batteries, especially for Li–NMC 811 full batteries.     

Design Strategies to Enable the Efficient Use of Sodium Metal Anodes in High-Energy Batteries

Sodium-based batteries have attracted considerable attention and are recognized as ideal candidates for large-scale and low-cost energy storage. Sodium (Na) metal anodes are considered as one of the most promising anodes for next-generation, high-energy, Na-based batteries owing to their high theoretical specific capacity (1166 mA h g⁻¹) and low standard electrode potential. Herein, an overview of the recent developments in Na metal anodes for high-energy batteries is provided. The high reactivity and large volume expansion of Na metal anodes during charge and discharge make the electrode/electrolyte interphase unstable, leading to the formation of Na dendrites, short cycle life, and safety issues. Design strategies to enable the efficient use of Na metal anodes are elucidated, including liquid electrolyte engineering, electrode/electrolyte interface optimization, sophisticated electrode construction, and solid electrolyte engineering. Finally, the remaining challenges and future research directions are identified. It is hoped that this progress report will shape a consistent view of this field and provide inspiration for future research to improve Na metal anodes and enable the development of high-energy sodium batteries.     

Strategies for fabrication,confinement and performance boost of Li2S in lithium-sulfur,silicon-sulfur & related batteries

Lithium-sulfur (Li-S) batteries based on elemental sulfur cathodes require the use of highly reactive metallic Li or Li alloy anodes in cell constructions. In order to match with safer Li-free anodes, lithium sulfide (Li₂S) has been studied as a promising alternative cathode material for lightweight Li and Li-ion batteries. However, intrinsically high electrical resistance, large first charge barrier, dissolution during cycling and polysulfide shuttle limit the electrochemical performance of Li₂S. In this review, we discuss various approaches for producing Li₂S-based nano- and micron-scale composite particles and standalone electrodes aiming to overcoming such challenges. In addition, we discuss strategies for electrolyte optimizations. Finally, we share our perspective on the gaps between the state-of-the art research demonstrations and the requirements for successful mass-market commercialization.     

Protected Lithium‐Metal Anodes in Batteries: From Liquid to Solid

High‐energy lithium‐metal batteries are among the most promising candidates for next‐generation energy storage systems. With a high specific capacity and a low reduction potential, the Li‐metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li‐metal anodes. Recent studies have shown that the performance and safety of Li‐metal anodes can be significantly improved via organic electrolyte modification, Li‐metal interface protection, Li‐electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid‐state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li‐metal batteries. Inspired by the bright prospects of solid Li‐metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li‐metal batteries, such as low ionic conductivity of the electrolyte and Li–electrolyte interfacial problems. Here, the approaches to protect Li‐metal anodes from liquid batteries to solid‐state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li‐metal anodes are discussed to facilitate the practical application of Li‐metal batteries.     

In situ and operando characterisation of Li metal – Solid electrolyte interfaces

The use of lithium metal as the negative electrode holds great promise for high energy density solid-state batteries (SSBs) of the future, but at the same time presents major technical challenges in their development. Li metal, with its high reactivity, soft and ductile nature, and propensity towards mechanical deformation during electrochemical cycling, is susceptible to the formation of various defects such as voids, cracks and filamentary deposits at the Li metal - solid electrolyte interface, that eventually cause rapid degradation of electrochemical cell performance. In order to gain insights into these interfacial processes and identify mechanisms for failure, in situ and operando characterisation approaches are essential. In this perspective, we present our opinions on the current state of such techniques, while highlighting the existing limitations and scope of these methods. We also endeavour to present opportunities for future research into developing and building on existing approaches to better evaluate the Li metal-solid electrolyte interface so as to guide the appropriate choice of materials to further enable efficient SSB architectures.     

Simultaneous High Ionic Conductivity and Lithium-Ion Transference Number in Single-Ion Conductor Network Polymer Enabling Fast-Charging Solid-State Lithium Battery

Developing solid-state electrolyte with sufficient ionic conduction and flexible-intimate interface is vital to advance fast-charging solid-state lithium batteries. Solid polymer electrolyte yields the promise of interfacial compatibility, yet its critical bottleneck is how to simultaneously achieve high ionic conductivity and lithium-ion transference number. Herein, single-ion conducting network polymer electrolyte (SICNP) enabling fast charging is proposed to positively realize fast lithium-ion locomotion with both high ionic conductivity of 1.1 × 10⁻³ S cm⁻¹ and lithium-ion transference number of 0.92 at room temperature. Experimental characterization and theoretical simulations demonstrate that the construction of polymer network structure for single-ion conductor not only facilitates fast hopping of lithium ions for boosting ionic kinetics, but also enables a high dissociation level of the negative charge for lithium-ion transference number close to unity. As a result, the solid-state lithium batteries constructed by coupling SICNP with lithium anodes and various cathodes (e.g., LiFePO₄, sulfur, and LiCoO₂) display impressive high-rate cycling performance (e.g., 95% capacity retention at 5 C for 1000 cycles in LiFePO₄|SICNP|lithium cell) and fast-charging capability (e.g., being charged within 6 min and discharged over than 180 min in LiCoO₂|SICNP|lithium cell). Our study provides a prospective direction for solid-state electrolyte that meets the lithium-ion dynamics for practical fast-charging solid-state lithium batteries.     

A Single-Ion Conducting Borate Network Polymer as a Viable Quasi-Solid Electrolyte for Lithium Metal Batteries

Lithium-ion batteries have remained a state-of-the-art electrochemical energy storage technology for decades now, but their energy densities are limited by electrode materials and conventional liquid electrolytes can pose significant safety concerns. Lithium metal batteries featuring Li metal anodes, solid polymer electrolytes, and high-voltage cathodes represent promising candidates for next-generation devices exhibiting improved power and safety, but such solid polymer electrolytes generally do not exhibit the required excellent electrochemical properties and thermal stability in tandem. Here, an interpenetrating network polymer with weakly coordinating anion nodes that functions as a high-performing single-ion conducting electrolyte in the presence of minimal plasticizer, with a wide electrochemical stability window, a high room-temperature conductivity of 1.5 × 10⁻⁴ S cm⁻¹, and exceptional selectivity for Li-ion conduction (t_Li+ = 0.95) is reported. Importantly, this material is also flame retardant and highly stable in contact with lithium metal. Significantly, a lithium metal battery prototype containing this quasi-solid electrolyte is shown to outperform a conventional battery featuring a polymer electrolyte.     

锂离子电池负极储锂材料的研究进展

储锂材料是影响锂离子电池性能的关键因素之一,已成为国际上锂离子电池材料研究领域的热点和重点。综述了锂离子电池负极储锂材料的研究进展,但非简单地重复负极储锂材料发展的全部研究。重点关注了三大类负极储锂材料的电化学特性、储锂机理和主要电化学改性途径,并指出了三类负极储锂材料存在的技术问题和今后的研究方向。     

Solid state lithium metal batteries – Issues and challenges at the lithium-solid electrolyte interface

Solid-state Li-ion batteries employing a metallic lithium anode in conjunction with an inorganic solid electrolyte (ISE) are expected to offer superior energy density and cycle life. The realization of these metrics critically hinges on the simultaneous optimization of the ISE and the two electrode/electrolyte interfaces. In this Opinion article, we provide an overview of the materials and interfacial challenges that limit the performance of solid-state lithium metal batteries (SSLMBs). Owing to the importance of the Li/ISE interface, we dedicate a large section of this article to discuss the mechanistic aspects of lithium deposition at the Li/ISE interface. We further discuss a few recently proposed mechanisms that rationalize the growth of lithium through ISEs. We conclude our review with a brief discussion on the anode-free approach for fabricating SSLMBs where metallic lithium is generated in-situ from pre-lithiated cathodes.     

Anode Interface Engineering and Architecture Design for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are considered as one of the most promising options to realize rechargeable batteries with high energy capacity. Previously, research has mainly focused on solving the polysulfides' shuttle, cathode volume changes, and sulfur conductivity problems. However, the instability of anodes in Li–S batteries has become a bottleneck to achieving high performance. Herein, the main efforts to develop highly stable anodes for Li–S batteries, mainly including lithium metal anodes, carbon‐based anodes, and alloy‐based anodes, are considered. Based on these anodes, their interfacial engineering and structure design are identified as the two most important directions to achieve ideal anodes. Because of high reactivity and large volume change during cycling, Li anodes suffer from severe side reactions and structure collapse. The solid electrolyte interphase formed in situ by modified electrolytes and ex situ artificial coating layers can enhance the interfacial stability of anodes. Replacing common Li foil with rationally designed anodes not only suppresses the formation of dendritic Li but also delays the failure of Li anodes. Manipulating the anode interface engineering and rationally designing anode architecture represents an attractive path to develop high‐performance Li–S batteries.     

Recent Advances in Energy Chemical Engineering of Next-Generation Lithium Batteries

Rechargeable lithium-ion batteries (LIBs) afford a profound impact on our modern daily life. However, LIBs are approaching the theoretical energy density, due to the inherent limitations of intercalation chemistry; thus, they cannot further satisfy the increasing demands of portable electronics, electric vehicles, and grids. Therefore, battery chemistries beyond LIBs are being widely investigated. Next-generation lithium (Li) batteries, which employ Li metal as the anode and intercalation or conversion materials as the cathode, receive the most intensive interest due to their high energy density and excellent potential for commercialization. Moreover, significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions, as well as to technological improvement. This review starts by summarizing the electrolytes for next-generation Li batteries. Key challenges and recent progress in lithium-ion, lithium–sulfur, and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science. Finally, possible directions for further development in Li batteries are presented. Next-generation Li batteries are expected to promote the sustainable development of human civilization.     

Dual‐Layered Film Protected Lithium Metal Anode to Enable Dendrite‐Free Lithium Deposition

Lithium metal batteries (such as lithium–sulfur, lithium–air, solid state batteries with lithium metal anode) are highly considered as promising candidates for next‐generation energy storage systems. However, the unstable interfaces between lithium anode and electrolyte definitely induce the undesired and uncontrollable growth of lithium dendrites, which results in the short‐circuit and thermal runaway of the rechargeable batteries. Herein, a dual‐layered film is built on a Li metal anode by the immersion of lithium plates into the fluoroethylene carbonate solvent. The ionic conductive film exhibits a compact dual‐layered feature with organic components (ROCO₂Li and ROLi) on the top and abundant inorganic components (Li₂CO₃ and LiF) in the bottom. The dual‐layered interface can protect the Li metal anode from the corrosion of electrolytes and regulate the uniform deposition of Li to achieve a dendrite‐free Li metal anode. This work demonstrates the concept of rational construction of dual‐layered structured interfaces for safe rechargeable batteries through facile surface modification of Li metal anodes. This not only is critically helpful to comprehensively understand the functional mechanism of fluoroethylene carbonate but also affords a facile and efficient method to protect Li metal anodes.     

Regulating Li-Ion Transport through Ultrathin Molecular Membrane to Enable High-Performance All-Solid-State–Battery

Solid-state lithium metal batteries with garnet-type electrolyte provide several advantages over conventional lithium-ion batteries, especially for safety and energy density. However, a few grand challenges such as the propagation of Li dendrites, poor interfacial contact between the solid electrolyte and the electrodes, and formation of lithium carbonate during ambient exposure over the solid-state electrolyte prevent the viability of such batteries. Herein, an ultrathin sub-nanometer porous carbon nanomembrane (CNM) is employed on the surface of solid-state electrolyte (SSE) that increases the adhesion of SSE with electrodes, prevents lithium carbonate formation over the surface, regulates the flow of Li-ions, and blocks any electronic leakage. The sub-nanometer scale pores in CNM allow rapid permeation of Li-ions across the electrode–electrolyte interface without the presence of any liquid medium. Additionally, CNM suppresses the propagation of Li dendrites by over sevenfold up to a current density of 0.7 mA cm⁻² and enables the cycling of all-solid-state batteries at low stack pressure of 2 MPa using LiFePO₄ cathode and Li metal anode. The CNM provides chemical stability to the solid electrolyte for over 4 weeks of ambient exposure with less than a 4% increase in surface impurities.     

Horizontal Growth of Lithium on Parallelly Aligned MXene Layers towards Dendrite‐Free Metallic Lithium Anodes

Although metallic lithium is an extremely promising anode for lithium‐based batteries due to its high theoretical capacity, the uncontrollable growth of lithium dendrites, in particular under deep stripping and plating, have stagnated its application. It is demonstrated that parallelly aligned MXene (Ti₃C₂T_x ) layers enable the efficient guiding of lithium nucleation and growth on the surface of 2D MXene nanosheets, giving rise to horizontal‐growth lithium anodes. Moreover, the inherent fluorine terminations in MXene afford a uniform and durable solid electrolyte interface with lithium fluoride at the anode/electrolyte interface, efficiently regulating electromigration of lithium ions. Thus, a dendrite‐free lithium anode with a long cycle life up to 900 h and excellent deep stripping–plating capabilities up to 35 mAh cm^?2 is achieved, which can further serve as an anode for a lithium metal battery, exhibiting high cycle stability up to 1000 cycles.     

Aliphatic Polycarbonate‐Based Solid‐State Polymer Electrolytes for Advanced Lithium Batteries: Advances and Perspective

Conventional liquid electrolytes based lithium‐ion batteries (LIBs) might suffer from serious safety hazards. Solid‐state polymer electrolytes (SPEs) are very promising candidate with high security for advanced LIBs. However, the quintessential frailties of pristine polyethylene oxide/lithium salts SPEs are poor ionic conductivity (≈10⁻⁸ S cm⁻¹) at 25 °C and narrow electrochemical window (<4 V). Many innovative researches are carried out to enhance their lithium‐ion conductivity (10⁻⁴ S cm⁻¹ at 25 °C), which is still far from meeting the needs of high‐performance power LIBs at ambient temperature. Therefore, it is a pressing urgency of exploring novel polymer host materials for advanced SPEs aimed to develop high‐performance solid lithium batteries. Aliphatic polycarbonate, an emerging and promising solid polymer electrolyte, has attracted much attention of academia and industry. The amorphous structure, flexible chain segments, and high dielectric constant endow this class of polymer electrolyte excellent comprehensive performance especially in ionic conductivity, electrochemical stability, and thermally dimensional stability. To date, many types of aliphatic polycarbonate solid polymer electrolyte are discovered. Herein, the latest developments on aliphatic polycarbonate SPEs for solid‐state lithium batteries are summarized. Finally, main challenges and perspective of aliphatic polycarbonate solid polymer electrolytes are illustrated at the end of this review.     

Considering Critical Factors of Li‐rich Cathode and Si Anode Materials for Practical Li‐ion Cell Applications

In order to keep pace with increasing energy demands for advanced electronic devices and to achieve commercialization of electric vehicles and energy‐storage systems, improvements in high‐energy battery technologies are required. Among the various types of batteries, lithium ion batteries (LIBs) are among the most well‐developed and commercialized of energy‐storage systems. LIBs with Si anodes and Li‐rich cathodes are one of the most promising alternative electrode materials for next‐generation, high‐energy batteries. Si and Li‐rich materials exhibit high reversible capacities of <2000 mAh g^?1 and >240 mAh g^‐1, respectively. However, both materials have intrinsic drawbacks and practical limitations that prevent them from being utilized directly as active materials in high‐energy LIBs. Examples for Li‐rich materials include phase distortion during cycling and side reactions caused by the electrolyte at the surface, and for Si, large volume changes during cycling and low conductivity are observed. Recent progress and important approaches adopted for overcoming and alleviating these drawbacks are described in this article. A perspective on these matters is suggested and the requirements for each material are delineated, in addition to introducing a full‐cell prototype utilizing a Li‐rich cathode and Si anode.     

Lithium garnets: Synthesis,structure, Li+ conductivity,Li+ dynamics and applications

Inorganic solid fast Li⁺ conductors based batteries are expected to overcome the limitations over safety concerns of flammable organic polymer electrolytes based Li⁺ batteries. Hence, an all-solid-state Li⁺ battery using non-flammable solid electrolyte have attracted much attention as next-generation battery. Therefore, in the development of all-solid-state lithium rechargeable batteries, it is important to search for a solid electrolyte material that has high Li⁺ conductivity, low electronic conductivity, fast charge transfer at the electrode interface and wide electrochemical window stability against potential electrodes and lithium metal. Hence, significant research effort must be directed towards developing novel fast Li⁺ conductors as electrolytes in all-solid-state lithium batteries. Among the reported inorganic solid Li⁺ conductive oxides, garnet-like structural compounds received considerable attention in recent times for potential application as electrolytes in all-solid-state lithium batteries. The focus of this review is to provide comprehensive overview towards the importance of solid fast lithium ion conductors, advantages of lithium garnets over other ceramic lithium ion conductors and understanding different strategies on synthesis of lithium garnets. Attempts have also been made to understand relationship between the structure, Li⁺ conduction and Li⁺ dynamics of lithium garnets. The status of lithium garnets as solid electrolyte in electrochemical devices like all-solid state lithium battery, lithium-air battery and sensor are also discussed.     

A Highly Reversible,Dendrite-Free Lithium Metal Anode Enabled by a Lithium-Fluoride-Enriched Interphase

Metallic lithium is the most competitive anode material for next-generation lithium (Li)-ion batteries. However, one of its major issues is Li dendrite growth and detachment, which not only causes safety issues, but also continuously consumes electrolyte and Li, leading to low coulombic efficiency (CE) and short cycle life for Li metal batteries. Herein, the Li dendrite growth of metallic lithium anode is suppressed by forming a lithium fluoride (LiF)-enriched solid electrolyte interphase (SEI) through the lithiation of surface-fluorinated mesocarbon microbeads (MCMB-F) anodes. The robust LiF-enriched SEI with high interfacial energy to Li metal effectively promotes planar growth of Li metal on the Li surface and meanwhile prevents its vertical penetration into the LiF-enriched SEI from forming Li dendrites. At a discharge capacity of 1.2 mAh cm⁻², a high CE of >99.2% for Li plating/stripping in FEC-based electrolyte is achieved within 25 cycles. Coupling the pre-lithiated MCMB-F (Li@MCMB-F) anode with a commercial LiFePO₄ cathode at the positive/negative (P/N) capacity ratio of 1:1, the LiFePO₄//Li@MCMB-F cells can be charged/discharged at a high areal capacity of 2.4 mAh cm⁻² for 110 times at a negligible capacity decay of 0.01% per cycle.     

Porous Materials Applied in Nonaqueous Li–O2 Batteries: Status and Perspectives

Porous materials possessing high surface area, large pore volume, tunable pore structure, superior tailorability, and dimensional effect have been widely applied as components of lithium–oxygen (Li–O₂) batteries. Herein, the theoretical foundation of the porous materials applied in Li–O₂ batteries is provided, based on the present understanding of the battery mechanism and the challenges and advantageous qualities of porous materials. Furthermore, recent progress in porous materials applied as the cathode, anode, separator, and electrolyte in Li–O₂ batteries is summarized, together with corresponding approaches to address the critical issues that remain at present. Particular emphasis is placed on the importance of the correlation between the function-orientated design of porous materials and key challenges of Li–O₂ batteries in accelerating oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) kinetics, improving the electrode stability, controlling lithium deposition, suppressing the shuttle effect of the dissolved redox mediators, and alleviating electrolyte decomposition. Finally, the rational design and innovative directions of porous materials are provided for their development and application in Li–O₂ battery systems.     

Hierarchical Interconnected Expanded Graphitic Ribbons Embedded with Amorphous Carbon: An Advanced Carbon Nanostructure for Superior Lithium and Sodium Storage

Carbon materials have attracted considerable attention as anodes for lithium‐ion and sodium‐ion batteries due to their low cost and environmental friendliness. This work reports an advanced carbon nanostructure that takes advantage of the chelation effect of glucose and metal ions, which ensures the uniform dispersion of metal in the precursor. Thus, an effective catalytic conversion from sp³ to sp² carbon occurs, enabling simultaneously formation of pores with catalyzed graphitic structures. Due to the low carbonization temperature and short carbonization time as well as the different catalytic degree of various metals, a series of expanded graphitic layers from 0.34 to 0.44 nm with defects and amorphous carbon structure are obtained. The structure not only offers accessible graphitic spacings for reversible lithium/sodium ion insertion, but also provides abundant active sites for lithium/sodium ion adsorption in the defects and amorphous structure. Moreover, the hierarchical interconnected porous structure combining graphitic ribbons is beneficial for fast electronic/ionic transport and favorable electrolyte permeation. More importantly, such advanced carbon materials prove their feasibility for balancing the pore structure and degree of graphitization. When serving as the electrode material for lithium‐ion and sodium‐ion batteries, excellent electrochemical performance along with fast kinetics and long cycle life is achieved.