Vertically Aligned Carbon Nanofibers on Cu Foil as a 3D Current Collector for Reversible Li Plating/Stripping toward High‐Performance Li–S Batteries

A vertically aligned carbon nanofiber (VACNF) array with unique conically stacked graphitic structure directly grown on a planar Cu current collector (denoted as VACNF/Cu) is used as a high‐porosity 3D host to overcome the commonly encountered issues of Li metal anodes. The excellent electrical conductivity and highly active lithiophilic graphitic edge sites facilitate homogenous coaxial Li plating/stripping around each VACNF and forming a uniform solid electrolyte interphase. The high specific surface area effectively reduces the local current density and suppresses dendrite growth during the charging/discharging processes. Meanwhile, this open nanoscale vertical 3D structure eliminates the volume changes during Li plating/stripping. As a result, highly reversible Li plating/stripping with high coulombic efficiency is achieved at various current densities. A low voltage hysteresis of 35 mV over 500 h in symmetric cells is achieved at 1 mA cm^?2 with an areal Li plating capacity of 2 mAh cm^?2, which is far superior to the planar Cu current collector. Furthermore, a Li–S battery using a S@PAN cathode and a lithium‐plated VACNF/Cu (VACNF/Cu@Li) anode with slightly higher capacity (2 mAh cm^?2) exhibits an excellent rate capability and high cycling stability with no capacity fading over 600 cycles.     

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.     

N,O-Codoped Carbon Nanosheet Array Enabling Stable Lithium Metal Anode

Lithium metal anodes hold great potential for next-generation high-energy batteries. However, the low Coulombic efficiency (CE) and dendritic growth during lithium metal plating/stripping cause short cycle life and deter its practical application. Herein, nitrogen, oxygen-codoped vertical carbon nanosheet arrays are constructed on Cu foil (NOCA@Cu) as the efficient host to improve CE and suppress Li dendrites through polymer interfacial self-assembly and morphology-preserved pyrolysis. Benefitting from numerous vertical porous channels with abundant lithiophilic heteroatom dopants, 3D structured NOCA@Cu host can guide Li nucleation and growth in a controlled manner, leading to dendrite-free Li deposition with high CE and long life cycles in both carbonate electrolyte and ether electrolyte, surpassing horizontal carbon-coated Cu and pure Cu hosts. Finite element simulation further reveals the structural function of vertical carbon arrays as not only directing Li plating in the nanoarray-constructed confined space but also homogenizing the distribution of ion concentration and electrical field throughout the 3D electrode. To demonstrate the practical application of lithiated NOCA@Cu anode, it is coupled with a commercial LiFePO₄ cathode, delivering high capacity and long-cycle stability with nearly 100% CE. The cost-effective, scalable, and efficient features render NOCA@Cu a promising Li host toward practical lithium metal batteries.     

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.     

Lithiophilic and Antioxidative Copper Current Collectors for Highly Stable Lithium Metal Batteries

Designing copper (Cu) current collectors is a convenient way to stabilize lithium (Li) metal anodes. However, Cu current collectors and their derived Li/Cu anodes still face several obstacles, including lithiophobic and oxidizable Cu surface, cumbersome anode fabrication process, and low Li utilization. Here, a formate-treatment strategy is presented to reconstruct Cu current collectors with a passivation layer covered Cu(110) surface. This method can easily be generalized to increase the lithiophilicity and oxidation resistibility of Cu current collectors. Using the formate-treated Cu nanowire network as an anode current collector, the full cell consisting of a LiFePO₄ cathode and Li/Cu anode with a low negative/positive capacity ratio delivers an excellent cycling performance with 74.8% capacity retention after 1000 cycles at 1 C. In addition, a concept of an upper current collector is introduced to simplify the manufacturing procedure of Li/Cu anodes. This work provides new insights into the design and construction of high-performance Li/Cu anodes.     

Prestoring Lithium into Stable 3D Nickel Foam Host as Dendrite‐Free Lithium Metal Anode

Lithium metal is considered a “Holy Grail” of anode materials for high‐energy‐density batteries. However, both dendritic lithium deposition and infinity dimension change during long‐term cycling have extremely restricted its practical applications for energy storage devices. Here, a thermal infusion strategy for prestoring lithium into a stable nickel foam host is demonstrated and a composite anode is achieved. In comparison with the bare lithium, the composite anode exhibits stable voltage profiles (200 mV at 5.0 mA cm^?2) with a small hysteresis beyond 100 cycles in carbonate‐based electrolyte, as well as high rate capability, significantly reduced interfacial resistance, and small polarization in a full‐cell battery with Li₄Ti₅O₁₂ or LiFePO₄ as counter electrode. More importantly, in addition to the fact that lithium is successfully confined in the metallic nickel foam host, uniform lithium plating/stripping is achieved with a low dimension change (merely ≈3.1%) and effective inhibition of dendrite formation. The mechanism for uniform lithium stripping/plating behavior is explained based on a surface energy model.     

Strategies in Structure and Electrolyte Design for High-Performance Lithium Metal Batteries

Lithium metal is the “holy grail” anode for next-generation high-energy rechargeable batteries due to its high capacity and lowest redox potential among all reported anodes. However, the practical application of lithium metal batteries (LMBs) is hindered by safety concerns arising from uncontrollable Li dendrite growth and infinite volume change during the lithium plating and stripping process. The formation of stable solid electrolyte interphase (SEI) and the construction of robust 3D porous current collectors are effective approaches to overcoming the challenges of Li metal anode and promoting the practical application of LMBs. In this review, four strategies in structure and electrolyte design for high-performance Li metal anode, including surface coating, porous current collector, liquid electrolyte, and solid-state electrolyte are summarized. The challenges, opportunities, perspectives on future directions, and outlook for practical applications of Li metal anode, are also discussed.     

Exploration of Metal Alloys as Zero-Resistance Interfacial Modification Layers for Garnet-Type Solid Electrolytes

A solid-state battery with a lithium-metal anode and a garnet-type solid electrolyte has been widely regarded as one of the most promising solutions to boost the safety and energy density of current lithium-ion batteries. However, lithiophobic property of garnet-type solid electrolytes hinders the establishment of a good physical contact with lithium metal, bringing about a large lithium/garnet interfacial resistance that has remained as the greatest issue facing their practical application in solid-state batteries. Herein, a melt-quenching approach is developed by which varieties of interfacial modification layers based on metal alloys can be coated uniformly on the surface of the garnet. It is demonstrated that with an ultrathin, lithiophilic AgSn_0.6Bi_0.4O_x coating the interfacial resistance can be eliminated, and a dendrite-free lithium plating and stripping on the lithium/garnet interface can be achieved at a high current density of 20 mA cm⁻². The results reveal that the uniform coating on the garnet surface and the facile lithium diffusion through the coating layer are two major reasons for the excellent electrochemical performances. The all-solid-state full cell consisting of the surface modified garnet-type solid electrolyte with a LiNi_0.8Mn_0.1Co_0.1O₂ cathode and a lithium–metal anode maintains 86% of its initial capacity after 1000 stable cycles at 1 C.     

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.     

Accommodation of Silicon in an Interconnected Copper Network for Robust Li‐Ion Storage

Silicon (Si)‐based materials are one of the most promising anodes to be applied in rechargeable lithium ion batteries. However, the active Si/electrolyte interface causes continuous side reactions and poor conductivity, which significantly decreases the cycling stability. Cu is the only metallic current collector that has been known to promote electron conduction and lithium‐ion transfer without alloying reaction occurrence. However, to the best current knowledge, scalable interface engineering incorporating Cu has not been reported. Herein, this conductive Cu interface (CCI) is constructed through a self‐assembly carbothermic reduction method to achieve efficient protection of Si/electrolyte interfaces while allowing for fast Li⁺ diffusion. The energy barrier of lithium‐ion diffusion through Cu is calculated to be 0.1965 eV, which is much lower than that through Au, Fe, and Ni films. Benefiting from the enhanced interfacial protection and kinetics of Si with CCI, a fading rate of only 0.068% is maintained for 1000 cycles and an aerial capacity of 4.78 mAh cm^?2 is achieved after 280 cycles, which is comparable to the industry standards required for practical application.     

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.     

Light-Driven Polymer-Based All-Solid-State Lithium-Sulfur Battery Operating at Room Temperature

Poly(ethylene oxide)-based polymer all-solid-state Li S battery is a promising candidate due to its high specific energy, good processability, and low cost. However, the poor room temperature ionic conductivity limits its further development. Here an innovative photothermal battery technology is proposed to realize the normal operation at room temperature. This design places the 3D Cu substrate with Cu/Si core-shell structures between Li anode and outer encapsulation glass, so that the light can come in and generate heat efficiently by utilizing the carrier nonradiative recombination of Si nano shell, then the heat quickly transfers to the battery system through Cu core. Once simulated sunlight irradiates, the battery achieves a fast reaction kinetics and superior photothermal conversion, thus realizing a lifespan of over 20 cycles with a capacity of 1089.9 mAh g⁻¹ at 0.2 C. Even on the actual sunlight irradiation, a high discharge/charge capacity of 1065.2/1036.5 mAh g⁻¹ is also reached, indicating an excellent reversible electrochemical process. Moreover, the 3D nanostructure can accommodate the fatal volume variation of lithium and reduce the effective current density, thus suppressing the dendrite nucleation and growth. This study will open the avenue to develop a room temperature polymer all-solid-state Li S battery using photothermal technology.     

Ultrafine Titanium Nitride Sheath Decorated Carbon Nanofiber Network Enabling Stable Lithium Metal Anodes

Nonuniform local electric field and few nucleation sites on the reactive interface tend to cause detrimental lithium (Li) dendrites, which incur severe safety hazards and hamper the practical application of Li metal anodes in batteries. Herein, a carbon nanofiber (CNF) mat decorated with ultrafine titanium nitride (TiN) nanoparticles (CNF‐TiN) as both current collector and host material is reported for Li metal anodes. Uniform Li deposition is achieved by a synergetic effect of lithiophilic TiN and 3D CNF configuration with a highly conductive network. Theoretical calculations reveal that Li prefers to be adsorbed onto the TiN sheath with a low diffusion energy barrier, leading to controllable nucleation sites and dendrite‐free Li deposits. Moreover, the pseudocapacitive behavior of TiN identified through kinetics analysis is favorable for ultrafast Li⁺ storage and the charge transfer process, especially under a high plating/stripping rate. The CNF‐TiN‐modified Li anodes deliver lower nucleation overpotential for Li plating and superior electrochemical performance under a large current density (200 cycles at 3 mA cm^?2) and high capacity (100 cycles with 6 mAh cm^?2), as well as a long‐running lifespan (>600 h). The CNF‐TiN‐based full cells using lithium iron phosphate and sulfur cathodes exhibit excellent cycling stability.     

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.     

A Periodic “Self‐Correction” Scheme for Synchronizing Lithium Plating/Stripping at Ultrahigh Cycling Capacity

Lithium (Li) metal can deliver the highest theoretical specific capacity among all lithium battery anodes, yet its application is significantly hindered due to a series of critical challenges (poor cycleability and safety risks, etc.), most of which are related to uncontrolled Li dendrite growth. However, the dendrite problem cannot be fully avoided because of a number of complicated multi‐physical field factors, especially under high cycling rate and high capacity conditions. An ideal situation is when the battery can automatically restore the uncontrolled dendrites growth itself, whenever it appears during the entire cycling lifespan; however, discussion on this issue is rare. A periodically conductive/dielectric lamella scaffold is developed for hosting Li metal to realize a “self‐correction” functionality, which can automatically synchronize Li deposition/stripping by periodically re‐homogenizing electric field distribution around irregular Li protrusions. Consequently, dendrite‐free Li plating/stripping with high Coulombic efficiency can be achieved even at 5 mA cm^?2 and an ultrahigh cycling capacity of 15 mAh cm^?2. Notably, a maximal cumulative plating capacity of 4000 mAh cm^?2 with Li utilization of 50% is realized, outperforming most recently reported results. This work provides new insights for designing future smart high‐performance metal anode batteries for real application.     

MXene-Based Anode-Free Magnesium Metal Battery

Rechargeable magnesium batteries (RMBs) are promising next-generation low-cost and high-energy devices. Among all RMBs, anode-free magnesium metal batteries that use in situ magnesium-plated current collectors as negative electrodes can afford optimal energy densities. However, anode-free magnesium metal batteries have remained elusive so far, as their practical application is plagued by low Mg plating/stripping efficiency due to nonuniform Mg deposition on conventional anode current collectors. Herein, for the first time, an anode-free Mg-metal battery is developed by employing a 3D MXene (Ti₃C₂T_x) film with horizontal Mg electrodeposition. The magnesiophilic oxygen and reactive fluorine terminations in MXene enable an enriched local magnesium-ion concentration and a durable magnesium fluoride-rich solid electrolyte interphase on the Ti₃C₂T_x film surface. Meanwhile, Ti₃C₂T_x MXene exhibits a high lattice geometrical fit with Mg (≈96%) to guide the horizontal electrodeposition of Mg. Consequently, the developed Ti₃C₂T_x film achieves reversible Mg plating/stripping with high Coulombic efficiencies (>99.4%) at high-current-density (5.0 mA cm⁻²) and high-Mg-utilization (50%) conditions. When this Ti₃C₂T_x film is coupled with a pre-magnesized Mo₆S₈ cathode, the anode-free Mg-metal full-cell prototype exhibits a volumetric energy density five times higher than its standard Mg-metal counterpart. This work provides insights into the rational design of anode current collectors to guide horizontal Mg electrodeposition for anode-free Mg metal batteries.     

A Chemically Engineered Porous Copper Matrix with Cylindrical Core–Shell Skeleton as a Stable Host for Metallic Sodium Anodes

Sodium (Na) metal is the most promising alternative for lithium metal as anode for the next‐generation energy storage systems. However, its practical implementation is hindered by the huge volume change and severe Na metal dendrite growth during electrochemical stripping/plating. Herein, the use of a chemically engineered porous copper (Cu) matrix as a stable host for metallic Na anode is presented. By treating the commercial Cu foam through a facile and cost‐effective method, a composite matrix consists of cylindrical core–shell skeleton is achieved, facilitating uniform impregnation and confinement of Na within the matrix pores promoted by the chemical interaction between Na and the matrix. The unique matrix's surface characteristic can divert the Na deposition from the skeleton towards the Na reservoirs within the pores, suppressing the volume change and mossy/dendritic Na growth. A stable Na cycling behavior is demonstrated in carbonate electrolyte without any additives at a high capacity up to 3 mAh cm^?2 with a current density up to 2 mA cm^?2. Moreover, electrochemical measurements of a full cell made of the Na composite matrix anode clearly reveal the superior performance at high rate (5C) over that using bare Na metal.     

Metallic Particles-Induced Surface Reconstruction Enabling Highly Durable Zinc Metal Anode

Aqueous zinc batteries usher in a renaissance due to their intrinsic security and cost effectiveness, bespeaking vast application foreground for large-scale energy storage system. However, uncontrolled dendrite growth along with hydrogen evolution severely restricts its reversibility and stability for practical application. Herein, the surface of Zn metal is reconstructed with metallic particles (In, Sn, In_0.2Sn_0.8) to diminish surface defects and regulate Zn deposition behavior. The alloyed In–Sn greatly activates the Zn surface for lower Zn adsorption energy barrier to expedite plating kinetics and confine Zn aggregation. Dense and uniform deposition of Zn on the reconstructed surface significantly prevents the Zn substrate from dendrites growth for catastrophic damage. Meanwhile, alloy layer embodies high hydrogen evolution overpotential, ensuring high plating and stripping efficiency for Zn anode. Consequently, In_0.2Sn_0.8 reconstructed surface realizes long-term lifespan up to 1800 h with low polarization (12 mV) at the condition of 1 mA cm⁻² and 1 mAh cm⁻². When paired with sodium vanadate (NVO) cathode, the full cell steady operates for a high-capacity retention of 94.0% after 5000 cycles at 5 A g⁻¹. This study provides new insights into the surface-defects dependent Zn deposition process and offers a guide for constructing stable surface for dendrite-free Zn growth.     

Large Cumulative Capacity Enabled by Regulating Lithium Plating with Metal–Organic Framework Layers on Porous Carbon Nanotube Scaffolds

The high specific capacity of lithium metal is ideal to meet the current demand in rechargeable batteries but lithium dendrites and irreversible volume expansions are major hurdles. 3D lithium host materials can alleviate these problems by lowering the current density with large surface areas and accommodating lithium metal in their pores. However, lithium dendrites are persistently observed because of sluggish lithium-ion diffusion through tortuous pores, resulting in clogging and thereby dendrite growth. Herein, layered metal–organic frameworks (MOFs) are deposited on carboxylated carbon nanotube (CNT) scaffolds via coordination bonding. The MOF layer on the outside of the CNT scaffold has augmented lithium insertion into the porous scaffolds (24 mAh cm⁻² at 8 mA cm⁻²) and lithium plating/stripping lifetime (over 1700 h with 20 mAh cm⁻² cycle⁻¹). MOF has pores large enough for lithium ions to permeate through, and its electronically insulating property creates capacitive effects, distributing lithium ions over the surface of the MOF layer to avoid dendrite growth and clogging during lithium plating. Outstanding volumetric and gravimetric capacities (≈940 mAh cm⁻³ and ≈980 mAh g⁻¹) along with exceptional cumulative capacity (≈4.9 Ah cm⁻²) are obtained. This promising approach can store lithium without dendrites to deliver high energy densities required for the current rechargeable batteries.     

Establishing the Preferential Adsorption of Anion-Dominated Solvation Structures in the Electrolytes for High-Energy-Density Lithium Metal Batteries

The practical application of Li metal batteries (LMBs) is severely hindered by the unstable solid electrolyte interface (SEI). In this work, it is revealed that the unstable SEI mainly originates from the kinetic instability of Li⁺-solvation structures in the electrolyte which can result in continuous electrolyte decomposition and nonuniform Li deposition. To address this issue, preferential adsorption of anion-dominated solvation complexes (A-Coms) are established by integrating preferentially adsorbed anions (NO₃⁻ and Li₂S₈) into the Li⁺-solvation structures. In these structures, the locations of the lowest unoccupied molecular orbital energy level shift from solvents to anions, rendering a relieved electrolyte decomposition and an anion-derived SEI formation. Meanwhile, the anions in the A-coms preferentially adsorb on the Li metal surfaces due to their stronger chemisorption capability toward lithium metal anodes (LMAs) compared to the solvent molecules, effectively shielding solvent molecules from parasitic reaction with LMAs. Furthermore, the anion-derived SEI exhibits high Li-ion conductivity and low Li atom adhesion energy, which can facilitate uniform Li deposition. Consequently, this electrolyte can enable a high Li plating/stripping Coulombic efficiency of 98.5% over 500 cycles and a stable cycling under realistic testing conditions with a high-energy-density of 310 W h kg⁻¹ based on a full cell configuration.