Lithium–Sulfur Batteries under Lean Electrolyte Conditions: Challenges and Opportunities

The development of energy‐storage devices has received increasing attention as a transformative technology to realize a low‐carbon economy and sustainable energy supply. Lithium–sulfur (Li–S) batteries are considered to be one of the most promising next‐generation energy‐storage devices due to their ultrahigh energy density. Despite the extraordinary progress in the last few years, the actual energy density of Li–S batteries is still far from satisfactory to meet the demand for practical applications. Considering the sulfur electrochemistry is highly dependent on solid‐liquid‐solid multi‐phase conversion, the electrolyte amount plays a primary role in the practical performances of Li–S cells. Therefore, a lean electrolyte volume with low electrolyte/sulfur ratio is essential for practical Li–S batteries, yet under these conditions it is highly challenging to achieve acceptable electrochemical performances regarding sulfur kinetics, discharge capacity, Coulombic efficiency, and cycling stability especially for high‐sulfur‐loading cathodes. In this Review, the impact of the electrolyte/sulfur ratio on the actual energy density and the economic cost of Li–S batteries is addressed. Challenges and recent progress are presented in terms of the sulfur electrochemical processes: the dissolution–precipitation conversion and the solid–solid multi‐phasic transition. Finally, prospects of future lean‐electrolyte Li–S battery design and engineering are discussed.     

A Strategy for Configuration of an Integrated Flexible Sulfur Cathode for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur batteries are regarded as promising candidates for energy storage devices owing to their high theoretical energy density. The practical application is hindered, however, by low sulfur utilization and unsatisfactory capacity retention. Herein, we present a strategy for configuration of the sulfur cathode, which is composed of an integrated carbon/sulfur/carbon sandwich structure on polypropylene separator that is produced using the simple doctor‐blade technique. The integrated electrode exhibits excellent flexibility and high mechanical strength. The upper and bottom carbon layers of the sandwich‐structured electrode not only work as double current collectors, which effectively improve the conductivity of the electrode, but also serve as good barriers to suppress the diffusion of the polysulfide and buffer the volume expansion of the active materials, leading to suppression of the shuttle effect and low self‐discharge behavior.     

Sulfur Cathodes Based on Conductive MXene Nanosheets for High‐Performance Lithium–Sulfur Batteries

Lithium–sulfur batteries are amongst the most promising candidates to satisfy emerging energy‐storage demands. Suppression of the polysulfide shuttle while maintaining high sulfur content is the main challenge that faces their practical development. Here, we report that 2D early‐transition‐metal carbide conductive MXene phases—reported to be impressive supercapacitor materials—also perform as excellent sulfur battery hosts owing to their inherently high underlying metallic conductivity and self‐functionalized surfaces. We show that 70 wt % S/Ti₂C composites exhibit stable long‐term cycling performance because of strong interaction of the polysulfide species with the surface Ti atoms, demonstrated by X‐ray photoelectron spectroscopy studies. The cathodes show excellent cycling performance with specific capacity close to 1200 mA h g^?1 at a five‐hour charge/discharge (C/5) current rate. Capacity retention of 80 % is achieved over 400 cycles at a two‐hour charge/discharge (C/2) current rate.     

Ferrocene‐Promoted Long‐Cycle Lithium–Sulfur Batteries

Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur‐cathode materials in lithium–sulfur (Li–S) batteries. To develop long‐cycle Li–S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well‐defined surface sites; thereby improving cycling stability and allowing study of molecular‐level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide‐confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation–π interactions between Li⁺ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene.     

Electrolytes for Rechargeable Lithium–Air Batteries

Lithium–air batteries are promising devices for electrochemical energy storage because of their ultrahigh energy density. However, it is still challenging to achieve practical Li–air batteries because of their severe capacity fading and poor rate capability. Electrolytes are the prime suspects for cell failure. In this Review, we focus on the opportunities and challenges of electrolytes for rechargeable Li–air batteries. A detailed summary of the reaction mechanisms, internal compositions, instability factors, selection criteria, and design ideas of the considered electrolytes is provided to obtain appropriate strategies to meet the battery requirements. In particular, ionic liquid (IL) electrolytes and solid‐state electrolytes show exciting opportunities to control both the high energy density and safety.     

Dual Protection of Sulfur by Carbon Nanospheres and Graphene Sheets for Lithium–Sulfur Batteries

Well‐confined elemental sulfur was implanted into a stacked block of carbon nanospheres and graphene sheets through a simple solution process to create a new type of composite cathode material for lithium–sulfur batteries. Transmission electron microscopy and elemental mapping analysis confirm that the as‐prepared composite material consists of graphene‐wrapped carbon nanospheres with sulfur uniformly distributed in between, where the carbon nanospheres act as the sulfur carriers. With this structural design, the graphene contributes to direct coverage of sulfur to inhibit the mobility of polysulfides, whereas the carbon nanospheres undertake the role of carrying the sulfur into the carbon network. This composite achieves a high loading of sulfur (64.2 wt %) and gives a stable electrochemical performance with a maximum discharge capacity of 1394 mAh g^?1 at a current rate of 0.1 C as well as excellent rate capability at 1 C and 2 C. The improved electrochemical properties of this composite material are attributed to the dual functions of the carbon components, which effectively restrain the sulfur inside the carbon nano‐network for use in lithium–sulfur rechargeable batteries.     

Sulfur‐Impregnated Core–Shell Hierarchical Porous Carbon for Lithium–Sulfur Batteries

Core–shell hierarchical porous carbon spheres (HPCs) were synthesized by a facile hydrothermal method and used as host to incorporate sulfur. The microstructure, morphology, and specific surface areas of the resultant samples have been systematically characterized. The results indicate that most of sulfur is well dispersed over the core area of HPCs after the impregnation of sulfur. Meanwhile, the shell of HPCs with void pores is serving as a retard against the dissolution of lithium polysulfides. This structure can enhance the transport of electron and lithium ions as well as alleviate the stress caused by volume change during the charge–discharge process. The as‐prepared HPC‐sulfur (HPC‐S) composite with 65.3 wt % sulfur delivers a high specific capacity of 1397.9 mA h g^?1 at a current density of 335 mA g^?1 (0.2 C) as a cathode material for lithium–sulfur (Li‐S) batteries, and the discharge capacity of the electrode could still reach 753.2 mA h g^?1 at 6700 mA g^?1 (4 C). Moreover, the composite electrode exhibited an excellent cycling capacity of 830.5 mA h g^?1 after 200 cycles.     

Liquid‐Free Lithium–Oxygen Batteries

Non‐aqueous lithium–oxygen batteries are considered as most advanced power sources, albeit they are facing numerous challenges concerning almost each cell component. Herein, we diverge from the conventional and traditional liquid‐based non‐aqueous Li–O₂ batteries to a Li–O₂ system based on a solid polymer electrolyte (SPE‐) and operated at a temperature higher than the melting point of the polymer electrolyte, where useful and most applicable conductivity values are easily achieved. The proposed SPE‐based Li‐O₂ cell is compared to Li–O₂ cells based on ethylene glycol dimethyl ether (glyme) through potentiodynamic and galvanostatic studies, showing a higher cell discharge voltage by 80 mV and most significantly, a charge voltage lower by 400 mV. The solid‐state battery demonstrated a comparable discharge‐specific capacity to glyme‐based Li–O₂ cells when discharged at the same current density. The results shown here demonstrate that the safer PEO‐based Li–O₂ battery is highly advantageous and can potentially replace the contingent of liquid‐based cells upon further investigation.     

Elemental‐Sulfur‐Mediated Facile Synthesis of a Covalent Triazine Framework for High‐Performance Lithium–Sulfur Batteries

A covalent triazine framework (CTF) with embedded polymeric sulfur and a high sulfur content of 62 wt % was synthesized under catalyst‐ and solvent‐free reaction conditions from 1,4‐dicyanobenzene and elemental sulfur. Our synthetic approach introduces a new way of preparing CTFs under environmentally benign conditions by the direct utilization of elemental sulfur. The homogeneous sulfur distribution is due to the in situ formation of the framework structure, and chemical sulfur impregnation within the micropores of CTF effectively suppresses the dissolution of polysulfides into the electrolyte. Furthermore, the triazine framework facilitates electron and ion transport, which leads to a high‐performance lithium–sulfur battery.     

Nickel–Iron Layered Double Hydroxide Hollow Polyhedrons as a Superior Sulfur Host for Lithium–Sulfur Batteries

We have designed and synthesized novel hollow Ni/Fe layered double hydroxide (LDH) polyhedrons as an advanced sulfur host for enhancing the performance of lithium–sulfur (Li–S) batteries. The Ni/Fe LDH host shows multiple advantages. First, the Ni/Fe LDH shells can provide sufficient sulfiphilic sites for chemically bonding with polysulfides. Second, the hollow architecture can provide sufficient inner space for both loading a large amount of sulfur and accommodating its large volumetric expansion. Moreover, once the active material is confined within the host, the shells could easily restrict the outward diffusion of polysulfides, guaranteeing prolonged cycle life even with high sulfur loading. As a result, the S@Ni/Fe LDH cathode has successfully solved the main issues related to sulfur electrodes, and it exhibits significantly improved electrochemical performances with prolonged life over 1000 cycles and excellent rate properties.     

Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have been recognized as promising substitutes for current energy‐storage technologies owing to their exceptional advantage in energy density. The main challenge in developing highly efficient and long‐life Li–S batteries is simultaneously suppressing the shuttle effect and improving the redox kinetics. Polar host materials have desirable chemisorptive properties to localize the mobile polysulfide intermediates; however, the role of their electrical conductivity in the redox kinetics of subsequent electrochemical reactions is not fully understood. Conductive polar titanium carbides (TiC) are shown to increase the intrinsic activity towards liquid–liquid polysulfide interconversion and liquid–solid precipitation of lithium sulfides more than non‐polar carbon and semiconducting titanium dioxides. The enhanced electrochemical kinetics on a polar conductor guided the design of novel hybrid host materials of TiC nanoparticles grown within a porous graphene framework (TiC@G). With a high sulfur loading of 3.5 mg cm^?2, the TiC@G/sulfur composite cathode exhibited a substantially enhanced electrochemical performance.     

Hollow Carbon Nanofibers Filled with MnO2 Nanosheets as Efficient Sulfur Hosts for Lithium–Sulfur Batteries

Lithium–sulfur batteries have been investigated as promising electrochemical‐energy storage systems owing to their high theoretical energy density. Sulfur‐based cathodes must not only be highly conductive to enhance the utilization of sulfur, but also effectively confine polysulfides to mitigate their dissolution. A new physical and chemical entrapment strategy is based on a highly efficient sulfur host, namely hollow carbon nanofibers (HCFs) filled with MnO₂ nanosheets. Benefiting from both the HCFs and birnessite‐type MnO₂ nanosheets, the MnO₂@HCF hybrid host not only facilitates electron and ion transfer during the redox reactions, but also efficiently prevents polysulfide dissolution. With a high sulfur content of 71 wt % in the composite and an areal sulfur mass loading of 3.5 mg cm^?2 in the electrode, the MnO₂@HCF/S electrode delivered a specific capacity of 1161 mAh g^?1 (4.1 mAh cm^?2) at 0.05 C and maintained a stable cycling performance at 0.5 C over 300 cycles.     

Enhanced Performance of a Lithium–Sulfur Battery Using a Carbonate‐Based Electrolyte

The lithium–sulfur battery is regarded as one of the most promising candidates for lithium–metal batteries with high energy density. However, dendrite Li formation and low cycle efficiency of the Li anode as well as unstable sulfur based cathode still hinder its practical application. Herein a novel electrolyte (1 m LiODFB/EC‐DMC‐FEC) is designed not only to address the above problems of Li anode but also to match sulfur cathode perfectly, leading to extraordinary electrochemical performances. Using this electrolyte, lithium|lithium cells can cycle stably for above 2000 hours and the average Coulumbic efficiency reaches 98.8 %. Moreover, the Li–S battery delivers a reversible capacity of about 1400 mAh g^?1_sulfur with retention of 89 % for 1100 cycles at 1 C, and a capacity above 1100 mAh g^?1_sulfur at 10 C. The more advantages of this cell system are its outstanding cycle stability at 60 °C and no self‐discharge phenomena.     

Sandwich‐like Catalyst–Carbon–Catalyst Trilayer Structure as a Compact 2D Host for Highly Stable Lithium–Sulfur Batteries

Herein, we propose the construction of a sandwich‐structured host filled with continuous 2D catalysis–conduction interfaces. This MoN‐C‐MoN trilayer architecture causes the strong conformal adsorption of S/Li₂S_x and its high‐efficiency conversion on the two‐sided nitride polar surfaces, which are supplied with high‐flux electron transfer from the buried carbon interlayer. The 3D self‐assembly of these 2D sandwich structures further reinforces the interconnection of conductive and catalytic networks. The maximized exposure of adsorptive/catalytic planes endows the MoN‐C@S electrode with excellent cycling stability and high rate performance even under high S loading and low host surface area. The high conductivity of this trilayer texture does not compromise the capacity retention after the S content is increased. Such a job‐synergistic mode between catalytic and conductive functions guarantees the homogeneous deposition of S/Li₂S_x, and avoids thick and devitalized accumulation (electrode passivation) even after high‐rate and long‐term cycling.     

Sulfur Encapsulated in a TiO2‐Anchored Hollow Carbon Nanofiber Hybrid Nanostructure for Lithium–Sulfur Batteries

A hollow carbon nanofiber hybrid nanostructure anchored with titanium dioxide (HCNF@TiO₂) was prepared as a matrix for effective trapping of sulfur and polysulfides as a cathode material for Li–S batteries. The synthesized composites were characterized and examined by X‐ray diffraction, nitrogen adsorption–desorption measurements, field‐emission scanning electron microscopy, scanning transmission electron microscopy, and electrochemical methods such as galvanostatic charge/discharge, rate performance, and electrochemical impedance spectroscopy tests. The obtained HCNF@TiO₂–S composite showed a clear core–shell structure with TiO₂ nanoparticles coating the surface of the HCNF and sulfur homogeneously distributed in the coating layer. The HCNF@TiO₂–S composite exhibited much better electrochemical performance than the HCNF–S composite, which delivered an initial discharge capacity of 1040 mA h g^?1 and maintained 650 mAh g^?1 after 200 cycles at a 0.5 C rate. The improvements of electrochemical performances might be attributed to the unique hybrid nanostructure of HCNF@TiO₂ and good dispersion of sulfur in the HCNF@TiO₂–S composite.     

Three‐Dimensional Hierarchical Constructs of MOF‐on‐Reduced Graphene Oxide for Lithium–Sulfur Batteries

A three‐dimensional (3D) hierarchical MOF‐on‐reduced graphene oxide (MOF‐on‐rGO) compartment was successfully synthesized through an in situ reduced and combined process. The unique properties of the MOF‐on‐rGO compartment combining the polarity and porous features of MOFs with the high conductivity of rGO make it an ideal candidate as a sulfur host in lithium–sulfur (Li‐S) batteries. A high initial discharge capacity of 1250 mAh g^?1 at a current density of 0.1 C (1.0 C=1675 mAh g^?1) was reached using the MOF‐on‐rGO based electrode. At the rate of 1.0 C, a high specific capacity of 601 mAh g^?1 was still maintained after 400 discharge–charge cycles, which could be ascribed to the synergistic effect between MOFs and rGO. Both the hierarchical structures of rGO and the polar pore environment of MOF retard the diffusion and migration of soluble polysulfide, contributing to a stable cycling performance. Moreover, the spongy‐layered rGO can buffer the volume expansion and contraction changes, thus supplying stable structures for Li‐S batteries.     

Achilles’ Heel of Lithium–Air Batteries: Lithium Carbonate

The lithium–air battery (LAB) is envisaged as an ultimate energy storage device because of its highest theoretical specific energy among all known batteries. However, parasitic reactions bring about vexing issues on the efficiency and longevity of the LAB, among which the formation and decomposition of lithium carbonate Li₂CO₃ is of paramount importance. The discovery of Li₂CO₃ as the main discharge product in carbonate‐based electrolytes once brought researchers to “the end of the idyll“ in the early 2010s. In the past few years, tremendous efforts have been made to understand the formation and decomposition mechanisms of Li₂CO₃, as well as to conceive novel chemical/material strategies to suppress the Li₂CO₃ formation and to facilitate the Li₂CO₃ decomposition. Moreover, the study on Li₂CO₃ in LABs is opening up a new research field in energy technology. Considering the rapid development and innumerous emerging issues, it is timely to recapitulate the current understandings, define the ambiguities and the scientific gaps, and discuss topics of high priority for future research, which is the aim of this Minireview.