Composite Lithium Metal Anodes with Lithiophilic and Low-Tortuosity Scaffold Enabling Ultrahigh Currents and Capacities in Carbonate Electrolytes

The practical application of lithium metal anode has been hindered by safety and cyclability issues due to the uncontrollable dendrite growth, especially during fast cycling and deep plating/stripping process. Here, a composite Li metal anode supported by periodic, perpendicular, and lithiophilic TiO₂/poly(vinyl pyrrolidone) (PVP) nanofibers via a facial rolling process is reported. TiO₂/PVP nanofibers with good Li affinity provide low-tortuosity and directly inward Li⁺ transport paths to facilitate Li nucleation and deposition under high areal capacities and current densities. The micrometer-scale interspaces between TiO₂/PVP walls offer enough space to circumvent the huge volume variation and avoid structure collapsing during the repeated deep Li plating/stripping. The unique structure enables stable cycling under ultrahigh currents (12 mA cm⁻²), and ultra-deep plating/stripping up to 60 mAh cm⁻² with a long cycle life in commercial carbonate electrolytes. The gassing behavior in operating pouch cells is observed using ultrasonic transmission mapping. When paired with LiFePO₄ (5 mAh cm⁻²), sulfur (3 mAh cm⁻²), and high-voltage LiNi_0.8Co_0.1Mn_0.1O₂ cathodes, the composite Li anodes deliver remarkably improved rate performance and cycling stability, demonstrating that it could be a promising strategy for balancing high-energy density and high-power density in Li metal batteries.     

Porosity‐ and Graphitization‐Controlled Fabrication of Nanoporous Silicon@Carbon for Lithium Storage and Its Conjugation with MXene for Lithium‐Metal Anode

Silicon (Si) and lithium metal are the most favorable anodes for high‐energy‐density lithium‐based batteries. However, large volume expansion and low electrical conductivity restrict commercialization of Si anodes, while dendrite formation prohibits the applications of lithium‐metal anodes. Here, uniform nanoporous Si@carbon (NPSi@C) from commercial alloy and CO₂ is fabricated and tested as a stable anode for lithium‐ion batteries (LIBs). The porosity of Si as well as graphitization degree and thickness of the carbon layer can be controlled by adjusting reaction conditions. The rationally designed porosity and carbon layer of NPSi@C can improve electronic conductivity and buffer volume change of Si without destroying the carbon layer or disrupting the solid electrolyte interface layer. The optimized NPSi@C anode shows a stable cyclability with 0.00685% capacity decay per cycle at 5 A g^?1 over 2000 cycles for LIBs. The energy storage mechanism is explored by quantitative kinetics analysis and proven to be a capacitance‐battery dual model. Moreover, a novel 2D/3D structure is designed by combining MXene and NPSi@C. As lithiophilic nucleation seeds, NPSi@C can induce uniform Li deposition with buffered volume expansion, which is proven by exploring Li‐metal deposition morphology on Cu foil and MXene@NPSi@C. The practical potential application of NPSi@C and MXene@NPSi@C is evaluated by full cell tests with a Li(Ni_0.8Co_0.1Mn_0.1)O₂ cathode.     

Plasma Enhanced Lithium Coupled with Cobalt Fibers Arrays for Advanced Energy Storage

Construction of high efficiency and stable Li metal anodes is extremely vital to the breakthrough of Li metal batteries. In this study, for the first time, groundbreaking in situ plasma interphase engineering is reported to construct high-quality lithium halides-dominated solid electrolyte interphase layer on Li metal to stabilize & protect the anode. Typically, SF₆ plasma-induced sulfured and fluorinated interphase (SFI) is composed of LiF and Li₂S, interwoven with each other to form a consecutive solid electrolyte interphase. Simultaneously, brand-new vertical Co fibers (diameter: ≈5 µm) scaffold is designed via a facile magnetic-field-assisted hydrothermal method to collaborate with plasma-enhanced Li metal anodes (SFI@Li/Co). The Co fibers scaffold accommodates active Li with mechanical integrity and decreases local current density with good lithiophilicity and low geometric tortuosity, supported by DFT calculations and COMSOL Multiphysics simulation. Consequently, the assembled symmetric cells with SFI@Li/Co anodes exhibit superior stability over 525 h with a small voltage hysteresis (125 mV at 5 mA cm⁻²) and improved Coulombic efficiency (99.7%), much better than the counterparts. Enhanced electrochemical performance is also demonstrated in full cells with commercial cathodes and SFI@Li/Co anode. The research offers a new route to develop advanced alkali metal anodes for energy storage.     

Dendrite‐Free Lithium Plating Induced by In Situ Transferring Protection Layer from Separator

Lithium (Li) metal anodes are regarded as a promising pathway to meet the rapidly growing requirements on high energy density cells, owing to their highest gravimetric capacity (3840 mAh g^?1) and their lowest redox potential. The application of Li metal anodes, however, is still hindered by undesired dendrites formation and endless consumption of liquid electrolyte due to a continuous reaction on interface of electrolyte/Li‐metal without a stable solid–electrolyte–interface (SEI) layer. A stable protection layer is formed on Li metal anode by in situ transferring the coating layer from polymer separator. The Li anode protection strategy is developed with an in situ formed protection layer transferred through the reduction of a coating layer on polymer separator. A PbZr_0.52Ti_0.48O₃ (PZT) coating layer on polypropylene (PP) separator is reduced by Li metal anode to produce a Pb metal containing composite layer, which could form Pb–Li alloy and adhere to the surface of Li metal anode after the reaction and improves the Li plating/stripping efficiency owing to the formation of a more homogenized electric field. Both the Li/Li symmetric cells and LiFePO₄/Li cells with this PZT precoated PP separators exhibit significantly improved Coulombic efficiency and cycling life.     

Regulating Uniform Li Plating/Stripping via Dual‐Conductive Metal‐Organic Frameworks for High‐Rate Lithium Metal Batteries

Lithium metal anodes show immense scope for application in high‐energy electronics and electric vehicles. Unfortunately, lithium dendrite growth and volume change leading to short lifespan and safety issues severely limit the feasibility of lithium metal batteries. A rational design of metal–organic framework (MOF)‐modified Li metal anode with optimized Li plating/stripping behavior via one‐step carbonization of ZIF‐67 is proposed. Experimental and theoretical simulation results reveal that carbonized MOFs with uniformly dispersed Co nanoparticles in N‐graphene (Co@N‐G) exhibit an electronic/ionic dual‐conductivity and significantly improved affinity with Li, and so serve as an ideal host for dendrite‐free lithium deposition, consequently leading to uniform lithium plating/stripping during cycling. As a result, the anode delivers highly stable cyclic performance with high coulombic efficiency (CE) at ultrahigh current densities (CE = 91.5% after 130 cycles at 10 mA cm^?2, and CE = 90.4% after 80 cycles at 15 mA cm^?2). Moreover, the practical applicability and functionality of such anodes are demonstrated through assembly of Li‐Co@N‐G/NCM full batteries exhibiting a long cycle life of 100 cycles with a high capacity retention of 92% at 1 C.     

Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries

Lithium (Li) metal has been considered as an important substitute for the graphite anode to further boost the energy density of Li‐ion batteries. However, Li dendrite growth during Li plating/stripping causes safety concern and poor lifespan of Li metal batteries (LMB). Herein, fluoroethylene carbonate (FEC) additives are used to form a LiF‐rich solid electrolyte interphase (SEI). The FEC‐induced SEI layer is compact and stable, and thus beneficial to obtain a uniform morphology of Li deposits. This uniform and dendrite‐free morphology renders a significantly improved Coulombic efficiency of 98% within 100 cycles in a Li | Cu half‐cell. When the FEC‐protected Li metal anode matches a high‐loading LiNi_0.5Co_0.2Mn_0.3O₂ (NMC) cathode (12 mg cm^?2), a high initial capacity of 154 mAh g^?1 (1.9 mAh cm^?2) at 180.0 mA g^?1 is obtained. This LMB with conversion‐type Li metal anode and intercalation‐type NMC cathode affords an emerging energy storage system to probe the energy chemistry of Li metal protection and demonstrates the material engineering of batteries with very high energy density.     

In Situ Construction of Lithium Silicide Host with Unhindered Lithium Spread for Dendrite-Free Lithium Metal Anode

Performance degradation and safety issue caused by Li dendrite growth and huge volume variation hinder the practical application of Li metal anode in high-energy-density lithium batteries. Li diffusion barrier of the host is a key parameter that determines the dendrite growth. Herein, a stable Li₂₁Si₅ alloy host with very low Li diffusion barriers is designed and prepared by an in situ metallurgical method using low-cost micron silicon precursor. The low diffusion barrier of Li₂₁Si₅ host enables a dendrite-free Li deposition behavior. It is revealed that the in-situ formed porous Li₂₁Si₅ host not only has high Li affinity, but also suppresses volume variation of the electrode effectively and thus keeps superior structural stability during Li stripping and plating processes. As a result, this new Li metal anode with Li₂₁Si₅ host exhibits promising cycle stability and rate capability with low polarization in both symmetric and full cells. This study opens new opportunities for using alloy-based materials as the hosts for Li composite anodes.     

Self-Assembled Tent-Like Nanocavities for Space-Confined Stable Lithium Metal Anode

Lithium metal is considered as a promising anode for its high energy density and low redox potential. However, dendrite growth and electrolyte-lithium reaction lead to poor cycling stability of lithium anodes. Herein, a space-confined strategy is proposed to realize stable Li metal anode by constructing a nonplanar interface with flexible tent-like nanocavities. The tent-like interface is achieved through the self-assembly of graphene oxide on zinc nanosheets, accompanied by the spontaneous formation of Zn O C bond. Remarkably, the Zn O C bond immobilizes the graphene oxide layer to ensure tent-like structural integrity, and shows excellent lithophilicity to induce homogeneous lithium deposition within nanocavities. Furthermore, the process of Li plating/stripping is confined inside tent-like nanocavities to effectively decrease electrolyte content contact with fresh Li, which reduces hazardous electrolyte-lithium reaction and thus eliminates continuous consumption of Li metal. Consequently, the symmetrical cells with the tent-like interface deliver excellent long cycling performance over 1600 h at 1 mA cm⁻², and full batteries show high-capacity retention of 94.6% after 3000 cycles at 5 C. This strategy provides a unique flexible tent-like interface to achieve stable lithium metal anode.     

Building Artificial Solid‐Electrolyte Interphase with Uniform Intermolecular Ionic Bonds toward Dendrite‐Free Lithium Metal Anodes

Li metal has been widely regarded as a promising anode for next‐generation batteries due to its high theoretical capacity and low electrochemical potential. The unstable solid‐electrolyte interphase (SEI) and uncontrollable dendrite growth, however, incur severe safety hazards and hamper the practical application of Li metal anodes. Herein, an advanced artificial SEI layer constructed by [LiNBH]_n chains, which are crosslinked and self‐reinforced by their intermolecular Li? N ionic bonds, is designed to comprehensively stabilize Li metal anodes on a molecular level. Benefiting from its polymer‐like structure, the [LiNBH]_n layer is flexible and effectively tolerates the volume change of Li metal anodes. In addition, this layer with high polarity in its structure, helps to regulate the homogeneous distribution of the Li⁺ flux on Li electrodes via the further formation of Li? N bonds. The designed [LiNBH]_n layer is electrically nonconductive but highly ionically conductive, thus facilitating Li⁺ diffusion and confining Li deposition beneath the layer. Therefore, under the protection of the [LiNBH]_n layer, the Li metal anodes exhibit stable cycling at a 3 mA cm^?2 for more than 700 h, and the full cells with high lithium iron phosphate and sulfur cathodes mass loading also present excellent cycling stability.     

Template-Sacrificed Hot Fusion Construction and Nanoseed Modification of 3D Porous Copper Nanoscaffold Host for Stable-Cycling Lithium Metal Anodes

Lithium (Li) metal anodes have been proposed as a promising candidate for high-energy-density electrode materials in secondary batteries. However, the dendrite growth and unstable electrode–electrolyte interfaces during Li plating/stripping are fatal to their practical applications. Herein, the construction of 3D porous Au/Cu nanoscaffold prepared via a convenient template-sacrificed hot fusion construction method and a nanoseed modification process as an effective Li metal hosting material are proposed. The Au/Cu nanoscaffold can spatially guide uniform deposition of Li metal free from the growth of Li dendrites due to the homogenous Li⁺ ion flux and negligible nucleation overpotential. Moreover, the Cu skeleton can relieve volume change and stabilize local current density during cycling processes. Benefiting from these advantages, the symmetric cells based on self-supported Li-filled Au/Cu (Li-Au/Cu) nanoscaffold electrodes present highly stable Li plating/stripping for more than 1000 h with a low voltage hysteresis less than 90 mV and a long lifespan over 1300 h at 1.0 mA cm^–2 in carbonate-based electrolytes. Impressively, the Li-Au/Cu nanoscaffold||LiFePO₄ full cells also exhibit exceptional cycling stability and rate performance. This work provides a promising strategy to construct dendrite-free lithium metal anodes toward high-performance lithium metal batteries.     

Nanoflake Arrays of Lithiophilic Metal Oxides for the Ultra‐Stable Anodes of Lithium‐Metal Batteries

A molten lithium infusion strategy has been proposed to prepare stable Li‐metal anodes to overcome the serious issues associated with dendrite formation and infinite volume change during cycling of lithium‐metal batteries. Stable host materials with superior wettability of molten Li are the prerequisite. Here, it is demonstrated that a series of strong oxidizing metal oxides, including MnO₂, Co₃O₄, and SnO₂, show superior lithiophilicity due to their high chemical reactivity with Li. Composite lithium‐metal anodes fabricated via melt infusion of lithium into graphene foams decorated by these metal oxide nanoflake arrays successfully control the formation and growth of Li dendrites and alleviate volume change during cycling. A resulting Li‐Mn/graphene composite anode demonstrates a super‐long and stable lifetime for repeated Li plating/stripping of 800 cycles at 1 mA cm^?2 without voltage fluctuation, which is eight times longer than the normal lifespan of a bare Li foil under the same conditions. Furthermore, excellent rate capability and cyclability are realized in full‐cell batteries with Li‐Mn/graphene composite anodes and LiCoO₂ cathodes. These results show a major advancement in developing a stable Li anode for lithium‐metal batteries.     

A Soft Lithiophilic Graphene Aerogel for Stable Lithium Metal Anode

The lithium metal anode is one of the most promising anodes for next‐generation high‐energy‐density batteries. However, the severe growth of Li dendrites and large volume expansion leads to rapid capacity decay and shortened lifetime, especially in high current density and high capacity. Herein, a soft 3D Au nanoparticles@graphene hybrid aerogel (Au? GA) as a lithiophilic host for lithium metal anode is proposed. The large surface area and interconnected conductive pathways of the Au? GA significantly decrease the local current density of the electrode, enabling uniform Li deposition. Furthermore, the 3D porous structure effectively accommodates the large volume expansion during Li plating/stripping, and the Li_xAu alloy serves as a solid solution buffer layer to completely eliminate the Li nucleation over‐potential. Symmetric cells can stably cycle at 8 mA cm^?2 for 8 mAh cm^?2 and exhibit ultra‐long cycling: 1800 h at 2 mA cm^?2 for 2 mAh cm^?2, and 1200 h at 4 mA cm^?2 for 4 mAh cm^?2, with low over‐potential. Full cells assemble with a Cu@Au? GA? Li anode and LiFePO₄ cathode, can sustain a high rate of 8 C, and retain a high capacity of 59.6 mAh g^?1 after 1100 cycles at 2 C.     

Constructing a High‐Strength Solid Electrolyte Layer by In Vivo Alloying with Aluminum for an Ultrahigh‐Rate Lithium Metal Anode

The serious safety issues caused by uncontrollable lithium (Li) dendrite growth, especially at high current densities, seriously hamper the rapid charging of Li metal‐based batteries. Here, the construction of Al–Li alloy/LiCl‐based Li anode (ALA/Li anode) is reported by displacement and alloying reaction between an AlCl₃‐ionic liquid and a Li foil. This layer not only has high ion‐conductivity and good electron resistivity but also much improved mechanical strength (776 MPa) as well as good flexibility compared to a common solid electrolyte interphase layer (585 MPa). The high mechanical strength of the Al–Li alloy interlayer effectively eliminates volume expansion and dendrite growth in Li metal batteries, so that the ALA/Li anode achieves superior cycling for 1600 h (2.0 mA cm^?2) and 1000 cycles at an ultrahigh current density (20 mA cm^?2) without dendrite formation in symmetric batteries. In lithium–sulfur batteries, the dense alloy layer prevents direct contact between polysulfides and Li metal, inhibiting the shuttle effect and electrolyte decomposition. Long cycling performance is achieved even at a high current density (4 C) and a low electrolyte/sulfur (6.0 µL mg^?1). This easy fabrication process provides a strategy to realize reliable safety during the rapid charging of Li‐metal batteries.     

Regulating Lithium Nucleation and Deposition via MOF‐Derived Co@C‐Modified Carbon Cloth for Stable Li Metal Anode

Lithium metal is an exciting anode candidate with extra high theoretical specific capacity for new high‐energy rechargeable batteries. However, uncontrolled Li deposition and an unsteady solid electrolyte interface seriously obstruct the commercial application of Li anodes in Li metal batteries. Herein, 3D carbon cloth (CC) supporting N‐doped carbon (CN) nanosheet arrays embedded with tiny Co nanoparticles (CC@CN‐Co) are employed as a lithiophilic framework to regulate homogenous Li nucleation/growth behavior in a working Li metal anode. The emergence of Li dendrites is supposed to be inhibited by the conductive 3D scaffold that reduces local current density. The uniform nucleation of Li can be guided by N‐containing functional groups as they have a strong interaction with Li atoms, and the tiny Co nanoparticles can provide active sites to guide Li deposition. As a result, the current CC@CN‐Co host exhibits Li dendrite–free features and stable cycling performance with a low overpotential (20 mV) throughout 800 h cycles. When paired with the typical LiFePO₄ (LFP) cathode, the assembled CC@CN‐Co@Li//LFP@C full cell exhibits outstanding rate capability and improved cycling performance.     

Electrical Conductivity Gradient Based on Heterofibrous Scaffolds for Stable Lithium‐Metal Batteries

The inability to guide the nucleation locations of electrochemically deposited Li has long been considered the main factor limiting the utilization of high‐energy‐density Li‐metal batteries. In this study, an electrical conductivity gradient interfacial host comprising 1D high conductivity copper nanowires and nanocellulose insulating layers is used in stable Li‐metal anodes. The conductivity gradient system guides the nucleation sites of Li‐metal to be directed during electrochemical plating. Additionally, the controlled parameter of the intermediate layer affects the highly stable Li‐metal plating. The electrochemical behavior is confirmed through experiments associated with the COMSOL Multiphysics simulation data. The distributed Li‐ion reaction flux resulting from the controlled electrical conductivity enables stable cycling for more than 250 cycles at 1 mA cm^?2. The gradient system effectively suppresses dendrite growth even at a high current density of 5 mA cm^?2 and ensures Li plating and stripping with ultra‐long‐term stability. To demonstrate the high‐energy‐density full‐cell application of the developed anode, it is paired with the LiNi_0.8Co_0.1Mn_0.1O₂ cathode. The cells demonstrate a high capacity retention of 90% with an extremely high Coulombic efficiency of 99.8% over 100 cycles. These results shed light on the formidable challenges involved in exploiting the engineering aspects of high‐energy‐density Li‐metal batteries.     

Stabilizing Polymer–Lithium Interface in a Rechargeable Solid Battery

Solid polymer electrolytes (SPEs) are promising candidates for developing high‐energy‐density Li metal batteries due to their flexible processability. However, the low mechanical strength as well as the inferior interfacial regulation of ions between SPEs and Li metal anode limit the suppress ion of Li dendrites and destabilize the Li anode. To meet these challenges, interfacial engineering aiming to homogenize the distribution of Li⁺/electron accompanied with enhanced mechanical strength by Mg₃N₂ layer decorating polyethylene oxide is demonstrated. The intermediary Mg₃N₂ in situ transforms to a mixed ion/electron conducting interlayer consisting of a fast ionic conductor Li₃N and a benign electronic conductor Mg metal, which can buffer the Li⁺ concentration gradient and level the nonuniform electric current distribution during cycling, as demonstrated by a COMSOL Multiphysics simulation. These characteristics endow the solid full cell with a dendrite‐free Li anode and enhanced cycling stability and kinetics. The innovative interface design will accelerate the commercial application of high‐energy‐density solid batteries.     

High Areal Capacity Dendrite-Free Li Anode Enabled by Metal–Organic Framework-Derived Nanorod Array Modified Carbon Cloth for Solid State Li Metal Batteries

Li metal is one of the most promising anode materials for high energy density batteries. However, uncontrollable Li dendrite growth and infinite volume change during the charge/discharge process lead to safety issues and capacity decay. Herein, a carbonized metal–organic framework (MOF) nanorod arrays modified carbon cloth (NRA-CC) is developed for uniform Li plating/stripping. The carbonized MOF NRAs effectively convert the CC from lithiophobic to lithiophilic, decreasing the polarization and ensuring homogenous Li nucleation. The 3D interconnected hierarchal CC provides adequate Li nucleation sites for reducing the local current density to avoid Li dendrite growth, and broadens internal space for buffering the volume change during Li plating/stripping. These characteristics afford a stable cycling of the NRA-CC electrode with ultrahigh Coulombic efficiencies of 96.7% after 1000 h cycling at 2 mA cm⁻² and a prolonged lifespan of 200 h in the symmetrical cell under ultrahigh areal capacity (12 mAh cm⁻²) and current (12 mA cm⁻²). The solid-state batteries assembled with the composite Li anode, high-voltage cathode (LiNi_0.5Co_0.2Mn_0.3O₂), and composite solid-state electrolyte also deliver excellent cyclic and rate performance at 25 °C. This work sheds fresh insights on the design principles of a dendrite-free Li metal anode for safe solid-state Li metal batteries.     

Lithium Induced Nano-Sized Copper with Exposed Lithiophilic Surfaces to Achieve Dense Lithium Deposition for Lithium Metal Anode

Li metal batteries have attracted extensive research attention because of their extremely high theoretical capacity. However, the commercialization of the Li metal batteries is hindered, as uncontrolled Li dendrites growth leads to safety concerns and a low coulombic efficiency. To suppress Li dendrites growth and achieve dense Li deposition, a lithiophilic 3D Cu host is designed for Li metal anode, in which the nano-sized Cu is in situ formed with the aid of infused Li metal. The fabricated Li metal anode exhibit a superior electrochemical stability than raw Li metal anode, and compact Li is maintained during cycling. The experimental results and density functional theory calculations demonstrate that the nano-sized Cu formed on the surface of the skeleton host shows highly exposed Cu (100) and Cu (110) surfaces, which exhibits a strong affinity toward Li, and effectively eliminates the formation of Li dendrites, leading to a dense Li deposition. With the strategy of adjusting exposed surfaces of Cu host, the optimized Li metal anode enhances the electrochemical performance of full cells, and concomitantly demonstrates their potential for future designs of next-generation Li metal anodes or Li-free anodes for Li metal batteries.     

A Stable Polymer-based Solid-State Lithium Metal Battery and its Interfacial Characteristics Revealed by Cryogenic Transmission Electron Microscopy

Solid-state lithium metal batteries (SSLMBs) are a promising candidate for next-generation energy storage systems due to their intrinsic safety and high energy density. However, they still suffer from poor interfacial stability, which can incur high interfacial resistance and insufficient cycle lifespan. Herein, a novel poly(vinylidene fluoride‑hexafuoropropylene)-based polymer electrolyte (PPE) with LiBF₄ and propylene carbonate plasticizer is developed, which has a high room-temperature ionic conductivity up to 1.15 × 10⁻³ S cm⁻¹ and excellent interfacial stability. Benefitting from the stable interphase, the PPE-based symmetric cell can operate for over 1000 h. By virtue of cryogenic transmission electron microscopy (Cryo-TEM) characterization, the high interfacial compatibility between Li metal anode and PPE is revealed. The solid electrolyte interphase is made up of an amorphous outer layer that can keep intimate contact with PPE and an inner Li₂O-dominated layer that can protect Li from continuous side reactions during battery cycling. A LiF-rich transition layer is also discovered in the region of PPE close to Li metal anode. The feasibility of investigating interphases in polymer-based solid-state batteries via Cryo-TEM techniques is demonstrated, which can be widely employed in future to rationalize the correlation between solid-state electrolytes and battery performance from ultrafine interfacial structures.     

Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium‐Sulfur Batteries

With the significant progress made in the development of cathodes in lithium‐sulfur (Li‐S) batteries, the stability of Li metal anodes becomes a more urgent challenge in these batteries. Here the systematic investigation of the stability of the anode/electrolyte interface in Li‐S batteries with concentrated electrolytes containing various lithium salts is reported. It is found that Li‐S batteries using LiTFSI‐based electrolytes are more stable than those using LiFSI‐based electrolytes. The decreased stability is because the N–S bond in the FSI^? anion is fairly weak and the scission of this bond leads to the formation of lithium sulfate (LiSO_x) in the presence of polysulfide species. In contrast, in the LiTFSI‐based electrolyte, the lithium metal anode tends to react with polysulfide to form lithium sulfide (LiS_x), which is more reversible than LiSO_x formed in the LiFSI‐based electrolyte. This fundamental difference in the bond strength of the salt anions in the presence of polysulfide species leads to a large difference in the stability of the anode‐electrolyte interface and performance of the Li‐S batteries with electrolytes composed of these salts. Therefore, anion selection is one of the key parameters in the search for new electrolytes for stable operation of Li‐S batteries.