High‐Performance All‐Solid‐State Lithium–Sulfur Batteries Enabled by Amorphous Sulfur‐Coated Reduced Graphene Oxide Cathodes

Safety and the polysulfide shuttle reaction are two major challenges for liquid electrolyte lithium–sulfur (Li–S) batteries. Although use of solid‐state electrolytes can overcome these two challenges, it also brings new challenges by increasing the interface resistance and stress/strain. In this work, the interface resistance and stress/strain of sulfur cathodes are significantly reduced by conformal coating ≈2 nm sulfur (S) onto reduced graphene oxide (rGO). An Li–S full cell consisting of an rGO@S‐Li₁₀GeP₂S₁₂‐acetylene black (AB) composite cathode is evaluated. At 60 °C, the all‐solid‐state Li–S cell demonstrates a similar electrochemical performance as in liquid organic electrolyte, with high rate capacities of 1525.6, 1384.5, 1336.3, 903.2, 502.6, and 204.7 mA h g^?1 at 0.05, 0.1, 0.5, 1.0, 2.0, and 5.0 C, respectively. It can maintain a high and reversible capacity of 830 mA h g^?1 at 1.0 C for 750 cycles. The uniform distribution of the rGO@S nanocomposite in the Li₁₀GeP₂S₁₂‐AB matrix generates uniform volume changes during lithiation/delithiation, significantly reducing the stress/strain, thus extending the cycle life. Minimization of the stress/strain of solid cells is the key for a long cycle life of all‐solid‐state Li–S batteries.     

All‐Solid‐State Printed Bipolar Li–S Batteries

Despite their potential advantages over currently widespread lithium‐ion batteries, lithium–sulfur (Li–S) batteries are not yet in practical use. Here, for the first time bipolar all‐solid‐state Li–S batteries (ASSLSBs) are demonstrated that exhibit exceptional safety, flexibility, and aesthetics. The bipolar ASSLSBs are fabricated through a solvent‐drying‐free, ultraviolet curing‐assisted stepwise printing process at ambient conditions, without (high‐temperature/high‐pressure) sintering steps that are required for inorganic electrolyte‐based all‐solid‐state batteries. Two thermodynamically immiscible and nonflammable gel electrolytes based on ethyl methyl sulfone (EMS) and tetraethylene glycol dimethyl ether (TEGDME) are used to address longstanding concerns regarding the grain boundary resistance of conventional inorganic solid electrolytes, as well as the polysulfide shuttle effect in Li–S batteries. The EMS gel electrolytes embedded in the sulfur cathodes facilitate sulfur utilization, while the TEGDME gel composite electrolytes serve as polysulfide‐repelling separator membranes. Benefiting from the well‐designed cell components and printing‐driven facile processability, the resulting bipolar ASSLSBs exhibit unforeseen advancements in bipolar cell configuration, safety, foldability, and form factors, which lie far beyond those achievable with conventional Li–S battery technologies.     

Building Lithiophilic Ion‐Conduction Highways on Garnet‐Type Solid‐State Li+ Conductors

The integration of highly conductive solid‐state electrolytes (SSEs) into solid‐state cells is still a challenge mainly due to the high impedance existing at the electrolyte/electrode interface. Although solid‐state garnet‐based batteries have been successfully assembled with the assistance of an intermediate layer between the garnet and the Li metal anode, the slow discharging/charging rates of the batteries inhibits practical applications, which require much higher power densities. Here, a crystalline sulfonated‐covalent organic framework (COF) thin layer is grown on the garnet surface via a simple solution process. It not only significantly improves the lithiophilicity of garnet electrolytes via the lithiation of the COF layer with molten Li, but also creates effective Li⁺ diffusion “highways” between the garnet and the Li metal anode. As a result, the interfacial impedance of symmetric solid‐state Li cells is significantly decreased and the cells can be operated at high current densities up to 3 mA cm^?2, which is difficult to achieve with current interfacial modification technologies for SSEs. The solid‐state Li‐ion batteries using LiFePO₄ cathodes, Li anodes, and COF‐modified garnet electrolytes thus exhibit a significantly improved rate capability.     

Rechargeable Solid‐State Li–Air and Li–S Batteries: Materials,Construction, and Challenges

Nonaqueous Li–air and Li–S batteries are attracting considerable interest because of their outstanding theoretical capacities and energy densities. However, despite the substantial progress in their development, safety remains an issue because of the flammability of their organic electrolytes. Moreover, the electrolyte volatilization of Li–air batteries and “shuttle effect” in Li–S batteries seriously hinder their development. The use of solid‐state Li–air and Li–S batteries is one of the best solutions. Nevertheless, many challenges remain in solid electrolytes, electrodes, and interfaces. In this review, a comprehensive discussion on the development of solid‐state Li–air and Li–S batteries is provided. The discussion begins with introduction of the progress in solid electrolytes, including their ionic conductivities and chemical stabilities. It then moves on to the cathodes of both batteries and the interface between electrolytes and electrodes. The reaction process inside the cathode is also presented. Suggestions for the optimization of composite cathodes and modification of the electrode–electrolyte interface are provided in the end. Intensive effort is required for the development of solid‐state Li–air and Li–S batteries in the future.     

Hard Carbon Anodes and Novel Electrolytes for Long‐Cycle‐Life Room Temperature Sodium‐Sulfur Full Cell Batteries

A novel combination of hard carbon anode sodium pre‐loading and a tailored electrolyte is used to prepare room temperature sodium‐sulfur full cell batteries. The electrochemical loading with sodium ions is realized in a specific mixture of diethyl carbonate, ethylene carbonate, and fluoroethylene carbonate electrolyte in order to create a first solid electrolyte interface (SEI) on the anode surface. Combining such anodes with a porous carbon/sulfur composite cathode results in full cells with a significantly decreased polysulfide shuttle when compared to half cells combined with metallic sodium anodes. Further optimization involves the use of Na₂S/P₂S₅ doped tetraethylene glycol dimethyl ether based electrolyte in the full cell for the formation of a second SEI, reducing polysulfide shuttle even further. More importantly, the electrochemical discharge processes in the cell are improved by adding this dissolved complexation agent to the electrolyte. As a result of this combination sodium‐sulfur cells with tailored cathode materials and electrolytes can achieve high discharge capacities up to 980 mAh g^?1_sulfur and 1000 cycles with 200 mAh g^?1_sulfur remaining capacity, at room temperature.     

Micro‐ and Mesoporous Carbide‐Derived Carbon–Selenium Cathodes for High‐Performance Lithium Selenium Batteries

Nanocomposites of selenium (Se) and ordered mesoporous silicon carbide‐derived carbon (OM‐SiC‐CDC) are prepared for the first time and studied as cathodes for lithium‐selenium (Li‐Se) batteries. The higher concentration of Li salt in the electrolytes greatly improves Se utilization and cell cycle stability. Se‐CDC shows significantly better performance characteristics than Se‐activated carbon nanocomposites with similar physical properties. Se‐CDC also exhibits better rate performance and cycle stability compared to similarly produced sulfur (S)–CDC for Li/S batteries.     

Enabling High‐Energy Solid‐State Batteries with Stable Anode Interphase by the Use of Columnar Silicon Anodes

All‐solid‐state batteries (ASSBs) with silicon anodes are promising candidates to overcome energy limitations of conventional lithium‐ion batteries. However, silicon undergoes severe volume changes during cycling leading to rapid degradation. In this study, a columnar silicon anode (col‐Si) fabricated by a scalable physical vapor deposition process (PVD) is integrated in all‐solid‐state batteries based on argyrodite‐type electrolyte (Li₆PS₅Cl, 3 mS cm^?1) and Ni‐rich layered oxide cathodes (LiNi_0.9Co_0.05Mn_0.05O₂, NCM) with a high specific capacity (210 mAh g^?1). The column structure exhibits a 1D breathing mechanism similar to lithium, which preserves the interface toward the electrolyte. Stable cycling is demonstrated for more than 100 cycles with a high coulombic efficiency (CE) of 99.7–99.9% in full cells with industrially relevant areal loadings of 3.5 mAh cm^?2, which is the highest value reported so far for ASSB full cells with silicon anodes. Impedance spectroscopy revealed that anode resistance is drastically reduced after first lithiation, which allows high charging currents of 0.9 mA cm^?2 at room temperature without the occurrence of dendrites and short circuits. Finally, in‐operando monitoring of pouch cells gave valuable insights into the breathing behavior of the solid‐state cell.     

Regulating the Hidden Solvation‐Ion‐Exchange in Concentrated Electrolytes for Stable and Safe Lithium Metal Batteries

Lithium–sulfur batteries are attractive for automobile and grid applications due to their high theoretical energy density and the abundance of sulfur. Despite the significant progress in cathode development, lithium metal degradation and the polysulfide shuttle remain two critical challenges in the practical application of Li–S batteries. Development of advanced electrolytes has become a promising strategy to simultaneously suppress lithium dendrite formation and prevent polysulfide dissolution. Here, a new class of concentrated siloxane‐based electrolytes, demonstrating significantly improved performance over the widely investigated ether‐based electrolytes are reported in terms of stabilizing the sulfur cathode and Li metal anode as well as minimizing flammability. Through a combination of experimental and computational investigation, it is found that siloxane solvents can effectively regulate a hidden solvation‐ion‐exchange process in the concentrated electrolytes that results from the interactions between cations/anions (e.g., Li⁺, TFSI^?, and S^2?) and solvents. As a result, it could invoke a quasi‐solid‐solid lithiation and enable reversible Li plating/stripping and robust solid‐electrolyte interphase chemistries. The solvation‐ion‐exchange process in the concentrated electrolytes is a key factor in understanding and designing electrolytes for other high‐energy lithium metal batteries.     

Constructing Multifunctional Interphase between Li1.4Al0.4Ti1.6(PO4)3 and Li Metal by Magnetron Sputtering for Highly Stable Solid‐State Lithium Metal Batteries

Due to high ionic conductivity and low cost, Li_1.4Al_0.4Ti_1.6(PO₄)₃ (LATP) has emerged as a promising solid‐state electrolyte for next‐generation lithium (Li) metal solid‐state batterie with high safety performance and energy density. However, the extremely high impedance and surface instability of LATP with Li metal retard its practical application. Herein, a novel method is proposed to construct an ultrathin ZnO layer that is tightly coated on the LATP pellets, surface (ZnO@LATP) via magnetron sputtering, which in situ reacts with Li to form a low electronic conductivity and multifunctional solid electrolyte interphase (SEI). The formed SEI can not only effectively lower the interfacial resistance, but also overcome the side reactions of LATP with the Li metal anode and suppress the Li dendrite growth. Specifically, the interface resistance decreases from 80 554 to 353 Ω and the overpotential reduces from 1 V to 20 mV. As a result, the Li/ZnO@LATP@ZnO/Li symmetric batteries can stably cycle for more than 2000 h without short circuit at 0.05 mA cm^?2 and Li/ZnO@LATP/LiFePO₄ batteries show excellent cycle stability for 200 cycles at 0.1 C. This work highlights the significance of multifunctional interphase between LATP and Li metal for improvement of interfacial impedance and instability.     

Ultrathin,Flexible Polymer Electrolyte for Cost‐Effective Fabrication of All‐Solid‐State Lithium Metal Batteries

All‐solid‐state batteries are promising candidates for the next‐generation safer batteries. However, a number of obstacles have limited the practical application of all‐solid‐state Li batteries (ASSLBs), such as moderate ionic conductivity at room temperature. Here, unlike most of the previous approaches, superior performances of ASSLBs are achieved by greatly reducing the thickness of the solid‐state electrolyte (SSE), where ionic conductivity is no longer a limiting factor. The ultrathin SSE (7.5 µm) is developed by integrating the low‐cost polyethylene separator with polyethylene oxide (PEO)/Li‐salt (PPL). The ultrathin PPL shortens Li⁺ diffusion time and distance within the electrolyte, and provides sufficient Li⁺ conductance for batteries to operate at room temperature. The robust yet flexible polyethylene offers mechanical support for the soft PEO/Li‐salt, effectively preventing short‐circuits even under mechanical deformation. Various ASSLBs with PPL electrolyte show superior electrochemical performance. An initial capacity of 135 mAh g^?1 at room temperature and the high‐rate capacity up to 10 C at 60 °C can be achieved in LiFePO₄/PPL/Li batteries. The high‐energy‐density sulfur cathode and MoS₂ anode employing PPL electrolyte also realize remarkable performance. Moreover, the ASSLB can be assembled by a facile process, which can be easily scaled up to mass production.     

In Situ Synthesis of a Hierarchical All‐Solid‐State Electrolyte Based on Nitrile Materials for High‐Performance Lithium‐Ion Batteries

A hierarchical all‐solid‐state electrolyte based on nitrile materials (SEN) is prepared via in situ synthesis method. This hierarchical structure is fabricated by in situ polymerizing the cyanoethyl polyvinyl alcohol (PVA‐CN) in succinonitrile (SN)‐based solid electrolyte that is filled in the network of polyacrylonitrile (PAN)‐based electrospun fiber membrane. The crosslinked PVA‐CN polymer framework is uniformly dispersed in the SN‐based solid electrolyte, which can strongly enhance its mechanical strength and keeps it in a quasi‐solid state even over the melting point. The electrospun fiber membrane efficiently reduces the thickness of SEN film besides a further improvement in strength. Because of the unique hierarchical structure and structure similarity among the raw materials, the prepared SEN film exhibits high room‐temperature ionic conductance (0.30 S), high lithium ion transference number (0.57), favorable mechanical strength (15.31 MPa), excellent safety, and good flexibility. Furthermore, the in situ synthesis ensures an excellent adhesion between SEN and electrodes, which leads to an outstanding electrochemical performance for the assembled LiFePO₄/SEN/Li cells. Both the superior performance of SEN and the simple fabricating process of SEN‐based all‐solid‐state cells make it potentially as one of the most promising electrolyte materials for next generation lithium‐ion batteries.     

Hybrid Lithium‐Sulfur Batteries with an Advanced Gel Cathode and Stabilized Lithium‐Metal Anode

The insulating nature of sulfur, polysulfide shuttle effect, and lithium‐metal deterioration cause a decrease in practical energy density and fast capacity fade in lithium‐sulfur (Li‐S) batteries. This study presents an integrated strategy for the development of hybrid Li‐S batteries based on a gel sulfur cathode, a solid electrolyte, and a protective anolyte composed of a highly concentrated salt electrolyte containing mixed additives. The dense solid electrolyte completely blocks polysulfide diffusion, and also makes it possible to investigate the cathode and anode independently. This gel cathode effectively traps the polysulfide active material while maintaining a low electrolyte to sulfur ratio of 5.2 mL g^?1. The anolyte effectively protects the Li metal and suppresses the consumption of liquid electrolyte, enabling stable long‐term cycling for over 700 h in Li symmetric cells. This advanced design can simultaneously suppress the polysulfide shuttle, protect Li metal, and reduce the liquid electrolyte usage. The assembled hybrid batteries exhibit remarkably stable cycling performance over 300 cycles with high capacity. Finally, surface‐sensitive techniques are carried out to directly visualize and probe the interphase formed on the surface of the Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) pellet, which may help stabilize the solid–liquid interface.     

In Situ Generation of Artificial Solid‐Electrolyte Interphases on 3D Conducting Scaffolds for High‐Performance Lithium‐Metal Anodes

Rational structure design of the current collector along with further engineering of the solid‐electrolyte interphases (SEI) layer is one of the most promising strategies to achieve uniform Li deposition and inhibit uncontrolled growth of Li dendrites. Here, a Li₂S layer as an artificial SEI with high compositional uniformity and high lithium ion conductivity is in situ generated on the surface of the 3D porous Cu current collector to regulate homogeneous Li plating/stripping. Both simulations and experiments demonstrate that the Li₂S protective layer can passivate the porous Cu skeleton and balance the transport rate of lithium ions and electrons, thereby alleviating the agglomerated Li deposition at the top of the electrode or at the defect area of the SEI layer. As a result, the modified current collector exhibits long‐term cycling of 500 cycles at 1 mA cm^?2 and stable electrodeposition capabilities of 4 mAh cm^?2 at an ultrahigh current density of 4 mA cm^?2. Furthermore, full batteries (LiFePO₄ as cathode) paired with this designed 3D anode with only ≈200% extra lithium show superior stability and rate performance than the batteries paired with lithium foil (≈3000% extra lithium). These explorations provide new strategies for developing high‐performance Li metal anodes.     

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Multiple‐internal‐reflection infrared spectroscopy allows for the study of thin‐film amorphous silicon electrodes in situ and in operando, in conditions typical of those used in Li‐ion batteries. It brings an enhanced sensitivity, and the attenuated‐total‐reflection geometry allows for the extraction of quantitative information. When electrodes are cycled in representative electrolytes, the simultaneously recorded infrared spectra give an insight into the solid/electrolyte interphase (SEI) composition. They also unravel the dynamic behavior of this SEI layer by quantitatively assessing its thickness, which increases during silicon lithiation and partially decreases during delithiation. Li‐ion solvation effects in the vicinity of the electrode indicate that lithium incorporation in the solid phase is the rate‐determining step of the electrochemical processes during lithiation. The lithiation of the active material also results in the irreversible consumption of a large quantity of hydrogen in the pristine material. Finally, the evolution of the electronic absorption of the electrode material suggests that lithium diffusion is much easier after the first lithiation than in the pristine material. Therefore, in situ Fourier‐transform infrared spectroscopy performed in a well‐suited configuration efficiently extracts original and quantitative pieces of information on the surface and bulk phenomena affecting Li‐ion electrodes during their operation in realistic conditions.     

Dynamic Visualization of Cathode/Electrolyte Evolution in Quasi‐Solid‐State Lithium Batteries

Solid‐state lithium–sulfur batteries (SSLSBs) are highly appealing for electrochemical energy devices because of their promising theoretical energy density. An intensive acquaintance of SSLS interfacial behavior is of importance in gaining fundamental knowledge of working/failure mechanisms and clarifying further optimized design of advanced batteries. Herein, a direct visualization of the evolution of both component and structure is present inside a working SSLSB. In situ Raman spectroscopy clearly sheds light on the potential‐dependent evolution of sulfur speciation via subtly fabricating the electrochemical cell. Moreover, the real‐time optical microscopic views show that the irreversible structure deformation of solid‐state electrolytes (SSEs), which results from the decomposition of dissolved polysulfides (PSs) and gas generation inside the SSE, directly causes the fracture of sulfur cathode with the cycling times increasing. Furthermore, by an atomic force microscopy study, the evolving structure and dynamic behavior of SSEs are directly captured at the nano/microscale and further elucidate the PS shuttling determining the mechanism stability of electrolyte. This work provides a straightforward monitoring of the compositional and morphological evolution, which contributes one to exploring the failure mechanisms and interfacial reactions for the cell performance enhancement.     

Cyclic Aminosilane‐Based Additive Ensuring Stable Electrode–Electrolyte Interfaces in Li‐Ion Batteries

Ni‐rich cathodes are considered feasible candidates for high‐energy‐density Li‐ion batteries (LIBs). However, the structural degradation of Ni‐rich cathodes on the micro‐ and nanoscale leads to severe capacity fading, thereby impeding their practical use in LIBs. Here, it is reported that 3‐(trimethylsilyl)‐2‐oxazolidinone (TMS‐ON) as a multifunctional additive promotes the dissociation of LiPF₆, prevents the hydrolysis of ion‐paired LiPF₆ (which produces undesired acidic compounds including HF), and scavenges HF in the electrolyte. Further, the presence of 0.5 wt% TMS‐ON helps maintain a stable solid–electrolyte interphase (SEI) at Ni‐rich LiNi_0.7Co_0.15Mn_0.15O₂ (NCM) cathodes, thus mitigating the irreversible phase transformation from layered to rock‐salt structures and enabling the long‐term stability of the SEI at the graphite anode with low interfacial resistance. Notably, NCM/graphite full cells with TMS‐ON, which exhibit an excellent discharge capacity retention of 80.4%, deliver a discharge capacity of 154.7 mAh g^?1 after 400 cycles at 45 °C.     

On the Capacity Losses Seen for Optimized Nano‐Si Composite Electrodes in Li‐Metal Half‐Cells

While the use of silicon‐based electrodes can increase the capacity of Li‐ion batteries considerably, their application is associated with significant capacity losses. In this work, the influences of solid electrolyte interphase (SEI) formation, volume expansion, and lithium trapping are evaluated for two different electrochemical cycling schemes using lithium‐metal half‐cells containing silicon nanoparticle–based composite electrodes. Lithium trapping, caused by incomplete delithiation, is demonstrated to be the main reason for the capacity loss while SEI formation and dissolution affect the accumulated capacity loss due to a decreased coulombic efficiency. The capacity losses can be explained by the increasing lithium concentration in the electrode causing a decreasing lithiation potential and the lithiation cut‐off limit being reached faster. A lithium‐to‐silicon atomic ratio of 3.28 is found for a silicon electrode after 650 cycles using 1200 mAhg^?1 capacity limited cycling. The results further show that the lithiation step is the capacity‐limiting step and that the capacity losses can be minimized by increasing the efficiency of the delithiation step via the inclusion of constant voltage delithiation steps. Lithium trapping due to incomplete delithiation consequently constitutes a very important capacity loss phenomenon for silicon composite electrodes.     

Unraveling the Intra and Intercycle Interfacial Evolution of Li6PS5Cl‐Based All‐Solid‐State Lithium Batteries

High‐performance rechargeable all‐solid‐state lithium metal batteries with high energy density and enhanced safety are attractive for applications like portable electronic devices and electric vehicles. Among the various solid electrolytes, argyrodite Li₆PS₅Cl with high ionic conductivity and easy processability is of great interest. However, the low interface compatibility between sulfide solid electrolytes and high capacity cathodes like nickel‐rich layered oxides requires many thorny issues to be resolved, such as the space charge layer (SCL) and interfacial reactions. In this work, in situ electrochemical impedance spectroscopy and in situ Raman spectroscopy measurements are performed to monitor the detailed interface evolutions in a LiNi_0.8Co_0.1Mn_0.1O₂ (NCM)/Li₆PS₅Cl/Li cell. Combining with ex situ characterizations including scanning electron microscopy and X‐ray photoelectron spectroscopy, the evolution of the SCL and the chemical bond vibration at NCM/Li₆PS₅Cl interface during the early cycles is elaborated. It is found that the Li⁺ ion migration, which varies with the potential change, is a very significant cause of these interface behaviors. For the long‐term cycling, the SCL, interfacial reactions, lithium dendrites, and chemo‐mechanical failure have an integrated effect on interfaces, further deteriorating the interfacial structure and electrochemical performance. This research provides a new insight on intra and intercycle interfacial evolution of solid‐state batteries.     

Interface Engineering of MXene Composite Separator for High‐Performance Li–Se and Na–Se Batteries

Selenium (Se), due to its high electronic conductivity and high energy density, has recently attracted considerable interest as a cathode material for rechargeable Li/Na batteries. However, the poor cycling stability originating from the severe shuttle effect of polyselenides hinders their practical applications. Herein, highly stable Li/Na–Se batteries are developed using ultrathin (≈270 nm, loading of 0.09 mg cm^?2) cetrimonium bromide (CTAB)/carbon nanotube (CNT)/Ti₃C₂T_x MXene hybrid modified polypropylene (PP) (CCNT/MXene/PP) separators. The hybrid separator can immobilize the polyselenides via enhanced Lewis acid–base interactions between CTAB/MXene and polyselenides, which is demonstrated by theoretical calculations and X‐ray photoelectron spectroscopy. The incorporation of CNT helps to improve the electrolyte infiltration and facilitate the ionic transport. In situ permeation experiments are conducted for the first time to visually study the behavior of polyselenides, revealing the prohibited shuttle effect and protected Li anode from corrosion with CCNT/MXene/PP separators. As a result, the Li–Se batteries with CCNT/MXene/PP separators deliver an outstanding cycling performance over 500 cycles at 1C with an extremely low capacity decay of 0.05% per cycle. Moreover, the hybrid separators also perform well in Na–Se batteries. This study develops a preferable separator–electrolyte interface and the concept can be applied in other conversion‐type battery systems.     

Novel Design Concepts of Efficient Mg‐Ion Electrolytes toward High‐Performance Magnesium–Selenium and Magnesium–Sulfur Batteries

Developing high‐voltage Mg‐compatible electrolytes (>3.0 V vs Mg) still remains to be the biggest R&D challenge in the area of nonaqueous rechargeable Mg batteries. Here, the key design concepts toward exploring new boron‐based Mg salts in a specific way of highlighting the implications of anions are proposed for the first time. The well‐defined boron‐centered anion‐based magnesium electrolyte (BCM electrolyte) is successfully presented by facile one‐step mixing of tris(2H‐hexafluoroisopropyl) borate and MgF₂ in 1,2‐dimethoxyethane, in which the structures of anions have been thoroughly investigated via mass spectrometry accompanied by NMR and Raman spectra. The first all‐round practical BCM electrolyte fulfills all requirements of easy synthesis, high ionic conductivity, wide potential window (3.5 V vs Mg), compatibility with electrophilic sulfur, and simultaneously noncorrosivity to coin cell assemblies. When utilizing the BCM electrolyte, the fast‐kinetics selenium/carbon (Se/C) cathode achieves the best rate capability and the sulfur/carbon (S/C) cathode exhibits an impressive prolonged cycle life than previously published reports. The BCM electrolyte offers the most promising avenue to eliminate the major roadblocks on the way to high‐voltage Mg batteries and the design concepts can shed light on future exploration directions toward high‐voltage Mg‐compatible electrolytes.