Nitrogen‐Doped Mesoporous Carbon Promoted Chemical Adsorption of Sulfur and Fabrication of High‐Areal‐Capacity Sulfur Cathode with Exceptional Cycling Stability for Lithium‐Sulfur Batteries

As one important component of sulfur cathodes, the carbon host plays a key role in the electrochemical performance of lithium‐sulfur (Li‐S) batteries. In this paper, a mesoporous nitrogen‐doped carbon (MPNC)‐sulfur nanocomposite is reported as a novel cathode for advanced Li‐S batteries. The nitrogen doping in the MPNC material can effectively promote chemical adsorption between sulfur atoms and oxygen functional groups on the carbon, as verified by X‐ray absorption near edge structure spectroscopy, and the mechanism by which nitrogen enables the behavior is further revealed by density functional theory calculations. Based on the advantages of the porous structure and nitrogen doping, the MPNC‐sulfur cathodes show excellent cycling stability (95% retention within 100 cycles) at a high current density of 0.7 mAh cm^‐2 with a high sulfur loading (4.2 mg S cm^‐2) and a sulfur content (70 wt%). A high areal capacity (≈3.3 mAh cm^‐2) is demonstrated by using the novel cathode, which is crucial for the practical application of Li‐S batteries. It is believed that the important role of nitrogen doping promoted chemical adsorption can be extended for development of other high performance carbon‐sulfur composite cathodes for Li‐S batteries.     

Gas Pickering Emulsion Templated Hollow Carbon for High Rate Performance Lithium Sulfur Batteries

A CO₂ in water nanoparticle stabilized Pickering emulsion is used to template micrometer sized hollow porous nitrogen doped carbon particles for high rate performance lithium sulfur battery. For the first time, nanoparticles serve the dual role of an emulsion stabilizer and a pore template for the shell, directly utilizing in situ generated CO₂ bubbles as template for the core. The minimalistic nature of this method does not require expensive surfactants or additional core templates. Upon polymerization of melamine formaldehyde onto CO₂, a robust polymer/silica composite shell is formed and transformed into a porous shell upon washing. The micrometer‐sized hollow morphology in combination with its nitrogen rich porous shell demonstrates impressive rate capabilities of 670 and 500 mAh g^?1 even at a high rate of 7C and 9C, respectively. This material also possesses excellent cycle durability, exhibiting a low capacity decay of 0.088%/cycle over 300 cycles. Measurement of the shuttle current and impedance provides interesting insight into the polysulfide mass transfer mechanism of hollow structured sulfur hosts.     

High Loading Sulfur Cathodes by Reactive-Type Polymer Tubes for High-Performance Lithium-Sulfur Batteries

Simultaneously attaining high gravimetric energy density (E_g) and volumetric energy density (E_v) in lithium-sulfur (Li–S) batteries is a longstanding challenge that has to be solved for practical application, which demands breakthroughs in electrode materials with optimized functionality and structure. Herein, anthraquinone-containing, reactive-type polymer tubes (PQT) that can be used to regulate the redox chemistry of sulfur species are designed and prepared for practical Li–S batteries. PQT favors a similar redox potential window as sulfur, which effectively facilitates the immobilization and conversion of sulfur species through a reversible lithiation/delithiation process. Its tubular structure and high tap density is vital to the fabrication of intact electrode with high sulfur loading and minimizing electrolyte intake during battery operation. With all these contributions, Li–S battery with PQT/S cathode exhibits a stable cycling capacity (73% at 2.0 C over 1000 cycles), remarkable rate performance (514.2 mAh g⁻¹ at 10 C), and a high areal capacity of 7.20 mAh g⁻¹ with high sulfur loading under lean electrolyte condition. More importantly, the assembled Li–S pouch cell delivers an E_g of 329 Wh kg⁻¹ and an E_v of 401 Wh L⁻¹, which meets the requirement for practical operation.     

A Flexible 3D Multifunctional MgO‐Decorated Carbon Foam@CNTs Hybrid as Self‐Supported Cathode for High‐Performance Lithium‐Sulfur Batteries

One of the critical challenges to develop advanced lithium‐sulfur (Li‐S) batteries lies in exploring a high efficient stable sulfur cathode with robust conductive framework and high sulfur loading. Herein, a 3D flexible multifunctional hybrid is rationally constructed consisting of nitrogen‐doped carbon foam@CNTs decorated with ultrafine MgO nanoparticles for the use as advanced current collector. The dense carbon nanotubes uniformly wrapped on the carbon foam skeletons enhance the flexibility and build an interconnected conductive network for rapid ionic/electronic transport. In particular, a synergistic action of MgO nanoparticles and in situ N‐doping significantly suppresses the shuttling effect via enhanced chemisorption of lithium polysulfides. Owing to these merits, the as‐built electrode with an ultrahigh sulfur loading of 14.4 mg cm^?2 manifests a high initial areal capacity of 10.4 mAh cm^?2, still retains 8.8 mAh cm^?2 (612 mAh g^?1 in gravimetric capacity) over 50 cycles. The best cycling performance is achieved upon 800 cycles with an extremely low decay rate of 0.06% at 2 C. Furthermore, a flexible soft‐packaged Li‐S battery is readily assembled, which highlights stable electrochemical characteristics under bending and even folding. This cathode structural design may open up a potential avenue for practical application of high‐sulfur‐loading Li‐S batteries toward flexible energy‐storage devices.     

Electrode Design for Lithium–Sulfur Batteries: Problems and Solutions

Pursuit of advanced batteries with high‐energy density is one of the eternal goals for electrochemists. Over the past decades, lithium–sulfur batteries (LSBs) have gained world‐wide popularity due to their high theoretical energy density and cost effectiveness. However, their road to the market is still full of thorns. Apart from the poor electronic conductivity of sulfur‐based cathodes, LSBs involve special multielectron reaction mechanisms associated with active soluble lithium polysulfides intermediates. Accordingly, the electrode design and fabrication protocols of LSBs are different from those of traditional lithium ion batteries. This review is aimed at discussing the electrode design/fabrication protocols of LSBs, especially the current problems on various sulfur‐based cathodes (such as S, Li₂S, Li₂S_x catholyte, organopolysulfides) and corresponding solutions. Different fabrication methods of sulfur‐based cathodes are introduced and their corresponding bullet points to achieve high‐quality cathodes are highlighted. In addition, the challenges and solutions of sulfur‐based cathodes including active material content, mass loading, conductive agent/binder, compaction density, electrolyte/sulfur ratio, and current collector are summarized and rational strategies are refined to address these issues. Finally, the future prospects on sulfur‐based cathodes and LSBs are proposed.     

3D Interconnected Porous Carbon Aerogels as Sulfur Immobilizers for Sulfur Impregnation for Lithium‐Sulfur Batteries with High Rate Capability and Cycling Stability

To eliminate capacity‐fading effects due to the loss of sulfur cathode materials as a result of polysulfide dissolution in lithium–sulfur (Li–S) cells, 3D carbon aerogel (CA) materials with abundant narrow micropores can be utilized as an immobilizer host for sulfur impregnation. The effects of S incorporation on microstructure, surface area, pore size distribution, and pore volume of the S/CA hybrids are studied. The electrochemical performance of the S/CA hybrids is investigated using electrochemical impedance spectroscopy, galvanostatical charge–discharge, and cyclic voltammetry techniques. The 3D porous S/CA hybrids exhibit significantly improved reversible capacity, high‐rate capability, and excellent cycling performance as a cathode electrode for Li–S batteries. The S/CA hybrid with an optimal incorporating content of 27% S shows an excellent reversible capacity of 820 mAhg^?1 after 50 cycles at a current density of 100 mAg^?1. Even at a current density of 3.2C (5280 mAg^?1), the reversible capacity of 27%S/CA hybrid can still maintain at 521 mAhg^?1 after 50 cycles. This strategy for the S/CA hybrids as cathode materials to utilize the abundant micropores for sulfur immobilizers for sulfur impregnation for Li–S battery offers a new way to solve the long‐term reversibility obstacle and provides guidelines for designing cathode electrode architectures.     

Accelerated Li+ Desolvation for Diffusion Booster Enabling Low-Temperature Sulfur Redox Kinetics via Electrocatalytic Carbon-Grazfted-CoP Porous Nanosheets

Lithium–sulfur (Li–S) batteries are famous for their high energy density and low cost, but prevented by sluggish redox kinetics of sulfur species due to depressive Li ion diffusion kinetics, especially under low-temperature environment. Herein, a combined strategy of electrocatalysis and pore sieving effect is put forward to dissociate the Li⁺ solvation structure to stimulate the free Li⁺ diffusion, further improving sulfur redox reaction kinetics. As a protocol, an electrocatalytic porous diffusion-boosted nitrogen-doped carbon-grafted-CoP nanosheet is designed via forming the N Co P active structure to release more free Li⁺ to react with sulfur species, as fully investigated by electrochemical tests, theoretical simulations and in situ/ex situ characterizations. As a result, the cells with diffusion booster achieve desirable lifespan of 800 cycles at 2 C and excellent rate capability (775 mAh g⁻¹ at 3 C). Impressively, in a condition of high mass loading or low-temperature environment, the cell with 5.7 mg cm⁻² stabilizes an areal capacity of 3.2 mAh cm⁻² and the charming capacity of 647 mAh g⁻¹ is obtained under 0 °C after 80 cycles, demonstrating a promising route of providing more free Li ions toward practical high-energy Li–S batteries.     

Electrocatalytic Interlayer with Fast Lithium–Polysulfides Diffusion for Lithium–Sulfur Batteries to Enhance Electrochemical Kinetics under Lean Electrolyte Conditions

Lithium–sulfur batteries are promising energy‐storage devices because of their high theoretical energy densities. For practical Li–S batteries, reducing the amount of electrolyte used is essential for achieving the high energy densities. However, reducing the electrolyte amount leads to severe performance degradation, mainly because of sluggish deposition of discharge products (Li₂S) and the accompanying passivation issue that arise from the insulating nature of Li₂S. In this study, a lightweight, robust interlayer, with a 3D open structure and a low surface area is designed and fabricated. The structure facilitates electrolyte infiltration without trapping too much electrolyte. Moreover, the electrocatalytic Co nanoparticles embedded in the skeleton surface within the interlayer effectively promote Li ion diffusion, polysulfides conversion, and Li₂S deposition, and therefore enhance the electrochemical kinetics under lean electrolyte conditions. The mechanisms involved in the interlayer effects are investigated by microstructural characterizations, electrochemical performance tests, density functional theory calculations, and in situ X‐ray diffraction characterization. These results show the feasibility of using an interlayer strategy to improve the electrochemical performances of Li–S batteries under lean electrolyte conditions to potentially increase the practical energy densities of Li–S batteries.     

Defective Graphitic Carbon Nitride Modified Separators with Efficient Polysulfide Traps and Catalytic Sites for Fast and Reliable Sulfur Electrochemistry

The serious shuttle effect of lithium-sulfur batteries limits the efficient realization of high rate charging and discharging under high sulfur loading in practical applications. Herein, this work reports a strong mitigation toward lithium polysulfide (LiPSs) adsorption/catalysis by introducing defective graphite phase carbon nitride (g-C₃N₄) as an effective additive. Without significant weight increase, the nitrogen deficient g-C₃N₄, in the form of ultrafine spindle-like nitrogen deficient g-C₃N_4−x (sCN), can be easily combined with commercial poly-propylene (PP) separators after hydrophilic modification of polydopamine, which corresponds to an ultralow overall weightiness contribution of 0.17 mg cm⁻². Physical/electrochemical characterizations and theoretical studies reveal that sCN exhibits strong electrostatic attraction with LiPSs by nitrogen defects and new formation of cyano groups near edges, thereby maintaining rapid and reliable Li S electrochemistry. Of particular importance is the chainmail catalyst design with separators that enable magic polysulfides adsorption effect and desirable thermostability/wettability, which guarantees the sCNPP-assembled cells with long and stable durability over 500 cycles at 5.0 C (capacity fading rate: 0.05% per cycle), and a high capability of 476 mAh g⁻¹ is obtained.     

Solid‐State Lithium–Sulfur Battery Enabled by Thio‐LiSICON/Polymer Composite Electrolyte and Sulfurized Polyacrylonitrile Cathode

Solid‐state lithium–sulfur battery (SSLSB) is attractive due to its potential for providing high energy density. However, the cell chemistry of SSLSB still faces challenges such as sluggish electrochemical kinetics and prominent “chemomechanical” failure. Herein, a high‐performance SSLSB is demonstrated by using the thio‐LiSICON/polymer composite electrolyte in combination with sulfurized polyacrylonitrile (S/PAN) cathode. Thio‐LiSICON/polymer composite electrolyte, which processes high ionic conductivity and wettability, is fabricated to enhance the interfacial contact and the performance of lithium metal anodes. S/PAN is utilized due to its unique electrochemical characteristics: electrochemical and structural studies combined with nuclear magnetic resonance spectroscopy and electron paramagnetic resonance characterizations reveal the charge/discharge mechanism of S/PAN, which is the radical‐mediated redox reaction within the sulfur grafted conjugated polymer framework. This characteristic of S/PAN can support alleviating the volume change in the cathode and maintaining fast redox kinetics. The assembled SSLSB full cell exhibits excellent rate performance with 1183 mAh g^?1 at 0.2 C and 719 mAh g^?1 at 0.5 C, respectively, and can accomplish 50 cycles at 0.1 C with the capacity retention of 588 mAh g^?1. The superior performance of the SSLSB cell rationalizes the construction concept and leads to considerations for the innovative design of SSLSB.     

A Synergistic System for Lithium–Oxygen Batteries in Humid Atmosphere Integrating a Composite Cathode and a Hydrophobic Ionic Liquid‐Based Electrolyte

Moisture in air is a major obstacle for realizing practical lithium‐air batteries. Here, we integrate a hydrophobic ionic liquid (IL)‐based electrolyte and a cathode composed of electrolytic manganese dioxide and ruthenium oxide supported on Super P (carbon black) to construct a promising system for Li‐O₂ battery that can be sustained in humid atmosphere (RH: 51%). A high discharge potential of 2.94 V and low charge potential of 3.34 V for 218 cycles are achieved. The outstanding performance is attributed to the synergistic effect of the unique hydrophobic IL‐based electrolyte and the composite cathode. This is the first time that such excellent performance is achieved in humid O₂ atmosphere and these results are believed to facilitate the realization of practical lithium‐air batteries.     

Honeycomb‐Like Spherical Cathode Host Constructed from Hollow Metallic and Polar Co9S8 Tubules for Advanced Lithium–Sulfur Batteries

The practical application of lithium‐sulfur (Li‐S) batteries remains remote because of rapid capacity fade caused by the low conductivity of sulfur, dissolution of intermediate lithium polysulfides, severe volumetric expansion, and slow redox kinetics of polysulfide intermediates. Here, to address these obstacles, a new sulfiphilic and highly conductive honeycomb‐like spherical cathode host constructed from hollow metallic and polar Co₉S₈ tubes is designed. Co₉S₈ can effectively bind polar polysulfides for prolonged cycle life, due to the strong chemisorptive capability for immobilizing the polysulfide species. The hollow structure, as the sulfur host, can further prevent polysulfide dissolution and offer sufficient space to accommodate the necessary volume expansion. Well‐aligned tubular arrays provide a conduit for rapid conduction of electrons and Li‐ions. More importantly, the experimental results and theoretical calculations show that Co₉S₈ plays an important catalytic role in improving the electrochemical reaction kinetics. When used as cathode materials for Li–S batteries, the S@Co₉S₈ composite cathode exhibits high capacity and an exceptional stable cycling life demonstrated by tests of 600 cycles at 1 C with a very low capacity decay rate of only ≈0.026% per cycle.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

Freestanding Bilayer Carbon–Sulfur Cathode with Function of Entrapping Polysulfide for High Performance Li–S Batteries

Li–S batteries benefit from numerous advantages such as high theoretical capacity, high energy density, and availability of an abundance of sulfur. However, commercialization of Li–S batteries has been impeded because of low loading amount of active materials and poor cycle performance. Herein, a freestanding bilayer carbon–sulfur (FBCS) cathode is reported with superior electrochemical performance at a high sulfur loading level (3 mg cm^?2). The top component of the FBCS cathode is composed of interlacing multiwalled carbon nanotubes (MWCNT) and the bottom component is made up of a mixed layer of sulfur imbedded in MWCNT and N‐doped porous carbon (NPC). The MWCNT layer (top part of FBCS cathode) blocks polysulfide migration from the cathode to the anode, and NPC in the bottom part of the FBCS cathode not only provides spacious active sites but also absorbs polysulfide by the nitrogen functional group. The designed novel FBCS cathode delivered a high initial discharge capacity of 964 and 900 mAh g^?1 at 0.5 and 1 C, respectively. It also displayed an excellent capacity retention of 83.1% at 0.5 C and 83.4% at 1 C after 300 cycles.     

A 3D Hybrid of Chemically Coupled Nickel Sulfide and Hollow Carbon Spheres for High Performance Lithium–Sulfur Batteries

Lithium–sulfur batteries are a promising next‐generation energy storage device owing to their high theoretical capacity and the low cost and abundance of sulfur. However, the low conductivity and loss of active sulfur material during operation greatly limit the rating capabilities and cycling stability of lithium–sulfur batteries. In this work, a unique sulfur host hybrid material comprising nanosized nickel sulfide (NiS) uniformly distributed on 3D carbon hollow spheres (C‐HS) is fabricated using an in situ thermal reduction and sulfidation method. In the hybrid material, the nanosized NiS provides a high adsorption capability for polysulfides and the C‐HS serves as a physical confinement for polysulfides and also a 3D electron transfer pathway. Moreover, NiS has strong chemical coupling with the C‐HS, favoring fast charge transfer and redox kinetics of the sulfur electrode. With a sulfur loading of up to 2.3 mg cm^?2, the hybrid material‐based lithium–sulfur batteries offer a capacity decay as low as 0.013% per cycle and a capacity of 695 mA h g^?1 at 0.5 C after 300 cycles. This unique 3D hybrid material with strong chemical coupling provides a promising sulfur host for high performance lithium–sulfur batteries.     

Activation of Oxygen‐Stabilized Sulfur for Li and Na Batteries

The sulfur‐based cathode materials suffer severely from poor cycling stability and low utilization, incurred by their stepwise reaction mechanism that generates polysulfide intermediates and the subsequent irreversible losses. In this work, those issues are significantly relieved by entrapping sulfur species in carbon host rich in oxygen functionalities. Sulfur species in such C/S composite are highly stabilized by their interaction with oxygen, and can deliver a reversible capacity of 508 mAh/(g of S) for 2000 cycles when coupled with Li, representing the best cycling stability up to date. More interestingly, extra capacity can be accessed by simply prelithiating the oxygen‐stabilized C/S composites down to 0.6 V for a few cycles, which enables a high capacity of 1621 mAh/(g of S) that eventually stabilizes at 820 mAh/(g of S) for 600 cycles. The mechanism for this electrochemical activation process is investigated with both spectroscopic and electrochemical techniques, which reveal that the inactive sulfur bonded to oxygen is liberated in the initial deep lithiation precycles and becomes electrochemically active. The oxygen‐stabilized sulfur can also be coupled with Na anode to form Na/S cell, confirming that the formation of S?O interaction in C/S composite generates promising sulfur‐based cathode materials for Li–S and Na–S batteries.     

Stabilizing Solid Electrolyte Interphases on Both Anode and Cathode for High Areal Capacity,High‐Voltage Lithium Metal Batteries with High Li Utilization and Lean Electrolyte

High‐energy‐density lithium metal batteries are considered the most promising candidates for the next‐generation energy storage systems. However, conventional electrolytes used in lithium‐ion batteries can hardly meet the demand of the lithium metal batteries due to their intrinsic instability for Li metal anodes and high‐voltage cathodes. Herein, an ester‐based electrolyte with tris(trimethylsilyl)phosphate additive that can form stable solid electrolyte interphases on the anode and cathode is reported. The additive decomposes before the ester solvent and enables the formation of P‐ and Si‐rich interphases on both electrodes that are ion conductive and robust. Thus, lithium metal batteries with a high‐specific‐energy of 373 Wh kg^?1 can exhibit a long lifespan of over 80 cycles under practical conditions, including a low negative/positive capacity ratio of 2.3, high areal capacity of 4.5 mAh cm^?2 for cathode, high‐voltage of 4.5 V, and lean electrolyte of 2.8 µL mAh^?1. A 4.5 V pouch cell is further assembled to demonstrate the practical application of the tris(trimethylsilyl)phosphate additive with an areal capacity of 10.2 and 9.4 mAh cm^?2 for the anode and cathode, respectively. This work is expected to provide an effective electrolyte optimizing strategy compatible with current lithium ion battery manufacturing systems and pave the way for the next‐generation Li metal batteries with high specific energy and energy density.     

Lithium Sulfonate Functionalization of Carbon Cathodes as a Substitute for Lithium Nitrate in the Electrolyte of Lithium–Sulfur Batteries

A method for grafting lithium sulfonate (LiSO₃) groups to carbon surfaces is developed and the resulting carbons are evaluated for their potential to reduce the lithium polysulfide (LiPS) shuttle in lithium–sulfur (Li–S) batteries, replacing the common electrolyte additive lithium nitrate (LiNO₃). The LiSO₃ groups are attached to the ordered mesoporous carbon (CMK3) surface via a three‐step procedure to synthesize LiSO₃‐CMK3 by bromomethylation, sodium sulfite (Na₂SO₃) substitution, and cation exchange. As a comparison, ethylenediamine (EN)‐substituted CMK3, EN‐CMK3, is also synthesized and tested. When used as a cathode in Li–S batteries, the unfunctionalized CMK3 suffers from strong LiPS shuttling as evidenced by its low initial Coulombic efficiencies (ICEs, <10%) compared to its functionalized derivatives EN‐CMK3 and LiSO₃‐CMK3 (ICEs >75%). Postcycling analysis reveals the benefits of cathode surface functionalization on the lithium anode via an attenuated LiPS shuttle. When monitored at open circuit, the functionalized cathodes maintain their cell voltages much better than the CMK3 control and concurrent electrochemical impedance spectroscopy reveals their higher total cell resistance, which provides evidence for a reduced LiPS shuttle in the vicinity of both electrodes. Overall, such surface groups show promise as cathode‐immobilized “lithium nitrate mimics.”