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The advancement of lithium‐ion batteries (LIBs) calls for superior electrolyte design to satisfy the booming demands of energy storage markets. Despite being typically indispensable in modern electrolytes, ethylene carbonate (EC) exhibits strong affinity with Li+ and derives organic‐rich SEI, leading to sluggish interfacial dynamics and unsatisfied rate capability. Here, we construct a kinetically favorable electrolyte based on linear carbonates (DMC) and fluoroethylene carbonate (FEC) with functional non‐solvating cosolvent, fluorobenzene (FB). Specifically, DMC and FEC, as weak binding solvents, show facile interfacial kinetics. FB enables a loose coordination chemistry through dipole‐dipole interaction, further lubricating Li+ desolvation and transport through SEI at interphase, which accelerates electrochemical kinetics and enables improved rate performance (257 mA h g−1 is achieved for graphite at 6 C). Moreover, the optimized electrolyte shows decent graphite compatibility, long‐term stability (75 % capacity retention after 350 cycles for NCM622/graphite pouch cells at 1 C) and wide‐temperature adaptability (−40~160 °C). This work reveals that dipole‐dipole interaction between non‐solvating cosolvents and solvents can effectively lower desolvation energy barrier and ultimately enable good rate capability, which provides a new avenue for designing EC‐free electrolyte in high‐rate LIBs. [ABSTRACT FROM AUTHOR]

Lithium metal batteries (LMBs) show great promise for achieving energy densities over 400 Wh·kg−1. However, highly flammable organic electrolytes are a long-lasting problem that triggers safety hazards and hinders the commercial application of LMBs. Here, a nonflammable diluted highly concentrated electrolyte (DHCE) with ethoxy(pentafluoro)cyclotriphosphazene (PFPN) as a diluent is developed to simultaneously achieve high safety and cycling stability of high-voltage LMBs. The optimal DHCE not only ensures reversible Li deposition/dissolution behavior with a superior average Coulombic efficiency (CE) over 99.1% on lithium metal anode (LMA), but also suppresses side reactions and stress crack on the LiCoO2 (LCO) under high cut-off voltage. The newly developed DHCE exhibits high thermal stability, showing complete nonflammability and reduced heat generation between the electrolyte and delithiated LCO/cycled LMA. This work offers an opportunity for rational designing nonflammable electrolytes toward high-voltage and safe LMBs. [ABSTRACT FROM AUTHOR]

The operation of lithium‐ion batteries (LIBs) at low temperatures (<−20 °C) is hindered by the low conductivity and high viscosity of conventional carbonate electrolytes. Methyl acetate (MA) has proven to be a competitive low‐temperature electrolyte solvent with low viscosity and low freezing point, but its interfacial stability is poor and remains elusive until now. Here, it is revealed thaat the reductive stability of MA‐based electrolytes is fundamentally governed by the anion‐prevailed solvation structure. Based on this framework, fluorobenzene is employed in the electrolyte to promote the entry of anions into the solvation shell via dipole‐dipole interactions and the generation of free MA, thus enhancing the lowest unoccupied molecular orbital energy of MA. The designed electrolyte enables LiCoO2 (LCO)/graphite cells to exhibit excellent cycling performance at −20 °C (90% retention after 1000 cycles at 1 C) and to remain 91% of their room‐temperature capacity at a super‐low temperature of −60 °C at 0.05 C. Thanks to the plentiful free MA, this electrolyte has a high conductivity (2.61 mS cm−1) at −60 °C and allows LCO/graphite cell to charge at −60 °C. This study offers the possibility of practical applications for those solvents with poor reductive stability and provides new approaches to designing advanced electrolytes for low‐temperature applications. [ABSTRACT FROM AUTHOR]

While recent work demonstrates the advantages of weakly solvating solvents in enhancing the cyclability of LMBs, both new designs and design strategies for high performance weakly solvating solvent, especially physicochemical properties, are still lacking. Here, we propose a molecular design to tune the solvating power and physicochemical properties of non‐fluorinated ether solvent. The resulting cyclopentylmethyl ether (CPME) have a weak solvating power and wide liquid‐phase temperature range. By optimizing the salt concentration, the CE is further promoted to 99.4 %. Besides, the improved electrochemical performance of Li−S battery in CPME‐based electrolytes is obtained at −20 °C. The Li||LFP (17.6 mg cm−2) battery with developed electrolyte maintains >90 % of the original capacity over 400 cycles. Our design concept for solvent molecule provides a promising pathway to non‐fluorinated electrolytes with weakly solvating power and wide temperature window for high‐energy‐density LMBs. [ABSTRACT FROM AUTHOR]

Exploring solid electrolytes (SEs) with high ionic conductivity, excellent chemical/electrochemical stability, and excellent compatibility with electrodes is important for promoting the development of all‐solid‐state batteries (ASSBs). Halogen‐rich lithium argyrodite electrolytes have received a lot of attention recently due to their ultrahigh room‐temperature lithium‐ion conductivity and relatively low cost. In this review, the properties of the halogen‐rich argyrodite electrolytes are presented in terms of their crystal structure, ionic conduction mechanism, and compatibilities with oxide cathode and Li‐metal anode. Secondly, the preparation process of SE film and the performances of ASSBs based on this electrolyte are summarized. Finally, the challenges and the next research directions of the electrolytes are proposed. Halogen‐rich lithium argyrodite electrolytes are one of the promising sulfide electrolytes, the collation of this paper can provide us with a better understanding of the current development status of this type of electrolyte and advance their further development. [ABSTRACT FROM AUTHOR]

Despite wide‐temperature tolerance and high‐voltage compatibility, employing propylene carbonate (PC) as electrolyte in lithium‐ion batteries (LIBs) is hampered by solvent co‐intercalation and graphite exfoliation due to incompetent solvent‐derived solid electrolyte interphase (SEI). Herein, trifluoromethylbenzene (PhCF3), featuring both specific adsorption and anion attraction, is utilized to regulate the interfacial behaviors and construct anion‐induced SEI at low Li salts' concentration (<1 m). The adsorbed PhCF3, showing surfactant effect on graphite surface, induces preferential accumulation and facilitated decomposition of bis(fluorosulfonyl)imide anions (FSI−) based on the adsorption–attraction–reduction mechanism. As a result, PhCF3 successfully ameliorates graphite exfoliation‐induced cell failure in PC‐based electrolyte and enables the practical operation of NCM613/graphite pouch cell with high reversibility at 4.35 V (96% capacity retention over 300 cycles at 0.5 C). This work constructs stable anion‐derived SEI at low concentration of Li salt by regulating anions–co‐solvents interaction and electrode/electrolyte interfacial chemistries. [ABSTRACT FROM AUTHOR]

Solid/solid interface is the major challenge for high‐performance solid‐state batteries. Solid electrolytes (SEs) play a crucial role in the fabrication of effective interfaces in solid‐state batteries. Herein, the electrolyte distribution with varied particle sizes is tuned to construct solid‐state batteries with excellent performance at different operating temperatures. Solid‐state batteries with the configuration S/L (small‐sized SE in composite cathode and large‐sized SE in electrolyte layer) show the best performance at room temperature (168 mA h g−1 at 0.2 C, retention of 99%, 100 cycles) and −20 °C (89 mA h g−1 at 0.05 C), while the configuration S/S displays better performance at elevated temperature. The superior performance of S/L battery is associated with faster lithium‐ion dynamics due to the better solid/solid interface between active materials and electrolytes. Moreover, the inferior performance at 60 °C is caused by the formation of voids and cracks in the electrolyte layer during cycling. In contrast, the S/S battery delivers superior performance at elevated operating temperature because of the integrated structure. This work confirms that tailoring electrolyte size has significant effect on fabricating all‐climate solid‐state batteries. [ABSTRACT FROM AUTHOR]

Fluorinated solvents emerge as a promising strategy to improve performance of lithium metal batteries (LMBs). However, most of them are prone to produce corrosive HF and deteriorate electrode interface, inducing cathode‐to‐anode detrimental crossover of transition metal‐ions. Here, fluorinated aromatic hydrocarbons in dimethyl carbonate (DMC)‐based diluted highly concentrated electrolyte (DHCE) are employed to juggle formation of HF and LiF, enabling stable cycling of high‐voltage LiNi0.7Co0.1Mn0.2O2 (NCM712) and LiCoO2 (LCO). The nature of aromatics in this carbonate‐based DHCE makes them difficult to undergo β‐hydrogen assisted defluorination, evidencing by the high energy barrier and high bond energy of β‐sites hydrogen. The advanced DHCE restrains HF formation but strengthens LiF formation, which not only suppresses impedance growth, transition‐metal dissolution, and stress crack on the cathode, but achieves highly reversible Li stripping/plating with an outstanding average Coulombic efficiency up to 99.3%. The Li||NCM712 cell and Li||LCO cell both exhibits superior cycling stability at high operation voltage. Even under stringent conditions, the 4.4 V Li||NCM712 full battery retains >95% of the initial capacity over 100 cycles, advancing practical high‐voltage LMBs. This study designs an efficient electrolyte that generates robust electrode/electrolyte interphases and restrains by‐products formation spontaneously, thus shedding new light on electrolyte toward applicable LMBs. [ABSTRACT FROM AUTHOR]

The advancements of lithium‐ion batteries indubitably call for advanced electrolytes with superior environmental adaptability and long‐term stability. Propylene carbonate (PC) proves to be a competitive solvent with the high permittivity and wide‐liquid range, while the application is intrinsically hindered by the poor graphite compatibility and high viscosity. Here, a PC‐based electrolyte with wide‐temperature range is developed by tuning the strength and topology of the Li+‐PC interactions via non‐solvating interactions without altering the solvation structure. Thus, the problem of graphite exfoliation caused by Li+‐PC co‐intercalation can be successfully mitigated. Consequently, such electrolyte shows compatibility with both graphite and high‐nickel cathode, exhibiting an expanded liquid range from −90 to 90 °C. This work, breaking from the traditional EC‐based formula, provides a new strategy for designing PC‐enabled electrolyte featuring high performance, wide‐temperature compatibility, and sustainability [ABSTRACT FROM AUTHOR]

Lithium (Li) metal is an ultra‐high specific capacity and low potential "holy grail" anode for developing high energy density rechargeable Li metal batteries (LMBs), but its practical application suffers from the low Coulombic efficiency (CE) and dendritic lithium growth due to its thermodynamic instability to organic solvents. Here, we report a new diluted high concentration electrolyte (DHCE) containing lithium bis(fluorosulfonyl)imide, triethyl phosphate and fluorobenzene cosolvent, which not only guarantees lithium metal anode (LMA) with an 98.4 % high average CE over 250 cycles but greatly improves Li||NMC622 cells property (70 % capacity retention after 200 cycles at C/3 current density). Therefore, this new electrolyte can provide more possibilities for developing high‐energy‐density LMBs. [ABSTRACT FROM AUTHOR]

An organoselenide compound, phenyl diselenide (PDSe), is employed as a soluble electrolyte additive to enhance the kinetics of a sulfurized polyacrylonitrile cathode, in which radical exchange in the solid–liquid interface forms dynamic S–Se bonds. Consequently, the PDSe assisted cathode exhibits enhanced battery performance in both ether and carbonate electrolytes. [ABSTRACT FROM AUTHOR]

The increasing demands for integration of renewable energy into the grid and urgently needed devices for peak shaving and power rating of the grid both call for low-cost and large-scale energy storage technologies. The use of secondary batteries is considered one of the most effective approaches to solving the intermittency of renewables and smoothing the power fluctuations of the grid. In these batteries, the states of the electrode highly affect the performance and manufacturing process of the battery, and therefore leverage the price of the battery. A battery with liquid metal electrodes is easy to scale up and has a low cost and long cycle life. In this progress report, the state-of-the-art overview of liquid metal electrodes (LMEs) in batteries is reviewed, including the LMEs in liquid metal batteries (LMBs) and the liquid sodium electrode in sodium-sulfur (Na-S) and ZEBRA (Na-NiCl2) batteries. Besides the LMEs, the development of electrolytes for LMEs and the challenge of using LMEs in the batteries, and the future prospects of using LMEs are also discussed. [ABSTRACT FROM AUTHOR]

Long charging times and poor low-temperature performance are two major challenges that hamper the widespread use of lithium-ion batteries in electrical devices. The electrolyte plays an important role in determining the charging time and operating temperature of batteries. Herein we demonstrate a weakly-solvating electrolyte consisting of 2.0 M lithium bis(fluorosulfonyl)imide in acetonitrile with fluorobenzene as the cosolvent. This combination is superior in terms of balancing the solvation/de-solvation of an electrolyte which simultaneously yields enhanced diffusion of Li+ in the bulk electrolyte and improved kinetics of Li+ de-solvation. In addition, we achieve a rapid interfacial diffusion of Li+ at the inorganic–polymeric solid electrolyte interphase, derived from fluorobenzene. Graphite half cells show a high specific capacity of 302.7 mA h g−1 at 8 C, long-term cycle life (91% retention after 1000 cycles at 5 C), and remarkable low temperature performance. Moreover, the NCM811 | graphite pouch cells also exhibit outstanding performance for fast-charging (201 mA h g−1 at 0.5 C and 167 mA h g−1 at 5 C) as well as outstanding cycling stability (80% retention after 500 cycles at 5 C). In summary, we provide design principles and experimental demonstration of next-generation electrolytes capable of fast charging and low-temperature operation. The weakly solvated electrolyte (2.0 M LiFSI-AN-FB) reported in this work has low Li+ de-solvation energy barrier and high ionic conductivity. Such an electrolyte addresses the issue of slow intercalation kinetics of Li+ under high-rate and low-temperature operation by balancing between solvation and de-solvation of electrolytes. [Display omitted] • A weakly-solvating electrolyte with balanced solvation/de-solvation is developed. • The designed electrolyte has fast de-solvation ability and Li+ transport kinetics. • Graphite half cells show a high specific capacity of 302.7 mA h g−1 even at 8 C. • This electrolyte has the potential to work at −40 °C. [ABSTRACT FROM AUTHOR]

Li 10 GeP 2 S 12 shows great potential as solid electrolytes for solid-state batteries due to its ultrahigh Li-ion conductivity. However, the high cost of Ge and the poor stability limit its applications. Replacing Ge with Sn can significantly lower the cost and maintains the high conductivity, while the corresponding Li 10 SnP 2 S 12 still suffers the low interfacial stability with the bare high voltage layered oxide cathodes. Herein, Li 10 SnP 2 S 12 with high Li-ion conductivity up to 4.79 mS cm−1 has been synthesized. All-solid-state battery using the cathode consisting of bare LiNi 0.6 Co 0.2 Mn 0.2 O 2 and Li 10 SnP 2 S 12 shows low capacities and poor cyclability due to side reactions between those two particles. To improve the interfacial stability, a highly conductive Li 3 InCl 6 electrolyte is introduced both in the cathode mixture and between the cathode layer and Li 10 SnP 2 S 12 solid electrolyte layer. This new configuration delivers superior electrochemical performances at different operating temperatures. It delivers high initial discharge capacities of 176.1 mAh g−1, 186.9 mAh g−1, and 73.7 mAh g−1 at 0.1C when operated at room temperature, 60 oC, and −20 oC, respectively. The superior battery performances are attributed to the excellent electrochemical stability of Li 3 InCl 6 electrolyte towards bare LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode. This work provides a guideline to design Li 10 SnP 2 S 12 -based all-solid-state lithium batteries with high energy density and long span life. [ABSTRACT FROM AUTHOR]

• Solvents and anions serve as regulators to mitigate TFP-Li+ interaction. • Multilevel regulation enhances TFP's reduction stability. • Developed nonflammable electrolytes contain high content of 83.3 vol% TFP. • The pouch-cells deliver remarkable ∼96.5 % capacity retention after 600 cycles. • The pouch-cells operate 6 months with a ∼99.98 % average CE. Carbonate-based electrolytes have been instrumental in extending the applicability of lithium-ion batteries (LIBs). However, their inherent high flammability contributes to frequent safety incidents, posing formidable challenges for the evolution of next-generation LIBs. Non-flammable electrolytes incorporating triethyl fluorophosphate (TFP) emerges as a promising solution. Nevertheless, TFP's suboptimal reduction stability and limited electronic shielding of its reduction product impede compatibility with graphite (Gr) electrode. To address these challenges, we employ solvents as primary regulators to mitigate TFP-Li+ interaction. Simultaneously, anions serve as alternative regulators, preventing the formation of TFP-Li+ clusters during the cells' dynamic operation. This multilevel regulation enhances TFP's reduction stability throughout the entire lifespan of cells. Developed nonflammable electrolytes with high content of 83.3 vol% TFP enable Gr anodes achieving approximately 92.7 % capacity retention after 200 cycles. Practical 1Ah Gr||LiNi 0.65 Co 0.15 Mn 0.2 O 2 pouch-cells deliver remarkable ∼96.5 % capacity retention after 600 cycles during 6 months of operation with a ∼99.98 % average CE. The extremely long-cycle calendar life and stability first verify the possibility of electrolytes containing high content TFP into commercial application. These findings not only introduce a fresh strategy for improving solvents' reduction stability, but also contribute to the advancement of safer LIBs, marking a significant step forward in battery research. [ABSTRACT FROM AUTHOR]

Fluorobenzene (FB) is identified as a well competitive candidate co-solvent due to the low-density and low-cost, but as a hydrocarbon, the high flammability may limit its application. Based on the DHCE concepts and the strategy of combining internal-external flame retardant, we successfully solve the flammable problem of FB and develop a non-flammable electrolyte with specific solvent structure. [Display omitted] Lithium-ion batteries with Ni-rich cathode and flammable carbonate electrolytes are breeding severe safety concerns which hinds their application in electric vehicles. Herein, by introducing the fluorobenzene (FB) with low-density and low-cost as a cosolvent and bridge solvents in triethyl phosphate (TEP)-based diluted high-concentration electrolytes (DHCEs) system, we design a non-flammable electrolyte with a special solvation structure containing internal-external flame retardants. This non-flammable electrolyte not only solves successfully the incompatibility problem of TEP-based electrolyte to the Li-metal anode (LMA) and the graphite (Gr) anode, but also ensures the stable cycling of Li||LiNi 0.7 Co 0. 1 Mn 0. 2 O 2 (86% capacity retention after 120 cycles) and Gr|| LiNi 0.7 Co 0. 1 Mn 0. 2 O 2 (75% capacity retention after 200 cycles) full cells. Such design opens up a new window for developing new electrolyte systems and building safer high-energy-density batteries. [ABSTRACT FROM AUTHOR]

A nonflammable methyl acetate (MA)-based diluted highly concentrated electrolyte (DHCE) was designed and prepared. The MA-based DHCE forms an anion-dominated solvation structure and a LiF-rich protective SEI, thus enhancing the thermodynamic and kinetic stability of the electrolyte simultaneously. This electrolyte enables LIBs to cycle at high voltage and −60 °C. [Display omitted] • Design a nonflammable MA-based DHCE with low-temperature and high-voltage tolerance. • The thermodynamic and kinetic stability of MA-based electrolytes is simultaneously enhanced. • The NCM65/graphite cell exhibits a capacity retention of 94.6 % after 300 cycles at 1 C and −20 °C. • The designed electrolyte enables NCM65/graphite cell to operate at a high voltage of 4.6 V and −60 °C. The operational demands of electronic devices in extreme environments present a significant challenge for lithium-ion batteries (LIBs) to function effectively at low temperatures. To address this challenge, methyl acetate (MA) has been considered as a potential electrolyte solvent. However, MA-based electrolytes show poor compatibility with graphite anodes and high flammability, which affects battery cycle life and brings safety risks. Herein, an advanced non-flammable MA-based diluted highly concentrated electrolyte (DHCE) is designed incorporating ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional diluent. The MA-based DHCE forms an anion-dominated solvation structure with improved thermodynamic stability. Moreover, PFPN synergizes with anions to form a protective LiF-rich solid electrolyte interphase (SEI), which effectively prevents continuous solvent decomposition. More importantly, PFPN can quench the free radical reaction and stop the spread of flames. This electrolyte enables LiNi 0.65 Co 0.15 Mn 0.2 O 2 (NCM65)/graphite full cell to maintain 94.6 % capacity retention after 300 cycles at 1 C and −20 °C. Moreover, it allows NCM65/graphite full cell to operate at a high voltage of 4.6 V and −60 °C. This work demonstrates the importance of co-solvents for electrolyte design and provides new routes for the development of LIBs operating in harsh conditions. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ag+ is successfully integrated into Li 5.5 PS 4.5 Cl 1.5 structure with improved ionic conductivity and better lithium metal stability. • A facial 3D host lithium metal with Ag and LiNO 3 particles on the surface is designed as the anode for this battery. • As-assembled all-solid-state lithium metal batteries showing much higher capacities and superior cyclability at different C-rates. Solid-state batteries combined with high-voltage layered cathode and lithium metal anode display good safety and high energy density, showing great potential as next-generation energy storage devices. However, the low ionic conductivity and poor stability with lithium metal of most solid electrolytes inhibit the development of solid-state lithium metal batteries. Herein, Ag+ is successfully integrated into Li 5.5 PS 4.5 Cl 1.5 structure with improved ionic conductivity and better lithium metal stability for the yielded Li 5.5-x Ag x PS 4.5 Cl 1.5 (x = 0, 0.02, 0.05, 0.10) electrolytes. Ag+ dopant is carefully tailored to achieve the optimal Li 5.45 Ag 0.05 PS 4.5 Cl 1.5 electrolyte with a high Li-ion conductivity of up to 9.1 mS cm−1 and a large CCD value of 1.8 mA cm−2. The corresponding battery with LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode and Li-In anode delivers a high initial discharge capacity of 154.9 mAh g−1 at 1.0C and maintains 94.5% of this value after 100 cycles. However, the same cathode shows low discharge capacities and fast degradation of capacities with bare lithium metal anode in solid-state batteries. A facial 3D host lithium metal with Ag and LiNO 3 particles on the surface is designed as the anode for this battery, showing much higher capacities and superior cyclability at different C-rates. The corresponding battery delivers discharge capacities of 140.6 mAh g−1 and 105.4 mAh g−1 when cycled at 0.1C and 0.5C. These superior electrochemical performances are attributed to the dual modification of Ag+ both in solid electrolytes and lithium metal anodes. [ABSTRACT FROM AUTHOR]

[Display omitted] • Flame retardants are introduced into electrolytes through a bridge co-solvent. • The designed electrolyte possesses biphasic fire extinguishing capability. • 2.9 Ah pouch cell shows only smoke under the severe nail penetration test. • The onset time of thermal runaway is delayed by 86 s under thermal abuse test. • The pouch cell exhibits a capacity retention of 87.5% after 1000 cycles at 0.5 C. Safety issues of LIBs are closely related to flammable carbonate electrolytes. Traditional strategies for nonflammable electrolytes involve soluble and coordinative flame retardants with limited choices, which interact with lithium ions and lead to deteriorated electrochemical performance. Meanwhile, single dosage of flame retardants fails to suppress ignition of both gas and liquid phases during thermal runaway (TR) of LIBs, thus generating multi-stage fire. Here, we introduce two flame retardants with high and low vapor pressure into carbonate electrolyte through a bridge co-solvent to obtain a non-flammable electrolyte with biphasic fire extinguishing capability. The designed electrolyte not only affords excellent electrochemical performance, but also simultaneously suppresses the combustion of flammable gases and liquid electrolytes. The Li[Ni 0.78 Co 0.10 Mn 0.12 ]O 2 | graphite pouch cell (2.90 Ah) empowered with such electrolyte exhibits outstanding cycling stability (87.5 % retention after 1000 cycles at 0.5 C) and shows only smoke under the severe nail penetration test as well as maximum temperature of TR reduced by 300 °C. What's more, the onset time of TR is delayed by 86 s under thermal abuse test. Furthermore, the pouch cell after 1000 cycles remains flameless under the nail penetration test. This work provides a promising path for expanding the selectivity of flame retardants and offers new strategy for designing advanced non-flammable electrolytes for safe LIBs. [ABSTRACT FROM AUTHOR]

The low Li-ion conductivity and poor interfacial compatibility towards cathode/anode materials of Li 6 PS 5 I solid electrolytes have significantly impeded their applications in all-solid-state batteries. This work developed a facial design strategy to improve the ionic conductivity and lithium metal compatibility of Li 6 PS 5 I electrolyte by the Sn-Cl dual doping. The optimal Li 6.6 P 0.8 Sn 0.2 S 5 I 0.6 Cl 0.4 electrolyte shows ultrahigh conductivity up to 0.96 mS/cm and enhanced lithium metal compatibility. The assembled battery using LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode and Li-In anode delivers a high initial discharge capacity of 175.7 mAh/g at 0.1C and maintains 79.2% after 100 cycles. Moreover, the corresponding battery using lithium metal anode displays a higher initial capacity (137.7 mAh/g vs. 112.7 mAh/g) and superior cyclability. The superior battery performances are attributed to the smaller interfacial resistances of those solid electrolyte-involved interfaces due to the Sn-Cl dual doping. This work demonstrates that the dual doping strategy is an effective route to exploring highly conductive Li 6 PS 5 I electrolytes. Highly conductive Li 6 PS 5 I electrolytes have been achieved by Sn-Cl dual doping with significantly enhanced Li-ion conductivity and lithium metal compatibility, which enables superior electrochemical performances for all-solid-state batteries. [Display omitted] [ABSTRACT FROM AUTHOR]

Chlorine-rich argyrodite Li 5.5 PS 4.5 Cl 1.5 presents great potential for the application of solid-state batteries (SSBs) due to the high ionic conductivity and relatively low cost. However, the effect of crystallinity for Li 5.5 PS 4.5 Cl 1.5 on the electrochemical performances of related solid-state batteries is unclear. Herein, the electrochemical performances of LiNi 0.8 Mn 0.1 Co 0.1 O 2 /SE/Li–In SSBs with crystalline and glass-ceramic Li 5.5 PS 4.5 Cl 1.5 (c - and gc -LPSC) electrolytes are carefully investigated. Electrochemical tests show that SSBs using c -LPSC electrolytes deliver higher capacities and better rate performances than that of gc -LPSC electrolytes at different operating temperatures due to the higher Li-ion conductivity of the former. Moreover, the optimized solid-state battery delivers an initial discharge capacity of 120.2 mAhg-1 at 5C and maintains 64% of the capacity after 3500 cycles under room temperature. At an elevated temperature (60 °C), a much higher discharge capacity of 145.5 mAh g-1 is achieved and 80.8% of the capacity is sustained after 500 cycles. This work unravels the influence of the crystallinity of argyrodite electrolytes on the intrinsic properties, providing a guiding significance for the construction of high-performance solid-state batteries. [Display omitted] • The influence of crystallinity of Li 5.5 PS 4.5 Cl 1.5 on battery performances is revealed. • Glass-ceramic Li 5.5 PS 4.5 Cl 1.5 affords superior electrochemical and mechanical stability. • Crystalline Li 5.5 PS 4.5 Cl 1.5 contributes to better capacity and rate performances. • Constructed SSB shows outstanding performance at −20 °C. [ABSTRACT FROM AUTHOR]

Lithium metal battery (LMB) is regarded as a rising star for next generation high energy density batteries. However, there is still a great challenge to achieve stable cycling of high-voltage LMBs, especially under practical conditions. Herein, we report a fluorobenzene-based (FB-based) diluted highly concentrated carbonate electrolyte with significantly improved physical and electrochemical properties. Employing FB as the diluent not only reduces the viscosity, density and cost of highly concentrated electrolyte, but also contributes to the formation of layer-like solid electrolyte interphase with enriched LiF. The collective superiority enables outstanding cycling stability of lithium metal anode. Consequently, Li||LiNi 0·6 Co 0·2 Mn 0·2 O 2 batteries with high areal capacity (3.6 mAh cm−2) based on such electrolyte show excellent cycling performance under a range of realistic conditions, including lean electrolyte (3 g Ah−1), low-temperature (−20 °C), and limited Li source (50 μm). This work provides a facile but effective method to achieve a stable high-voltage LMBs and demonstrates its potential in practical application. [Display omitted] • Fluorobenzene dilutes highly concentrated carbonate electrolytes. • Fluorobenzene endows electrolyte unique interfacial chemistry. • Modified electrolyte applies for high-voltage lithium metal batteries. • Full cell obtains excellent cycling performance under practical conditions. [ABSTRACT FROM AUTHOR]