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The Li5.5PS4.5Cl1.5 electrolyte gains significant attention due to its ultrahigh ionic conductivity and cost-effectiveness in halogen-rich lithium argyrodite solid electrolytes. The conventional synthetic method for obtaining the electrolyte involves mechanical milling followed by post-annealing. However, these synthesis methods typically involve high milling speeds, elevated temperatures, and prolonged durations, resulting in both high energy consumption and potential damage to the electrolyte. In this study, we successfully obtained Li5.5PS4.5Cl1.5 with a high conductivity of 7.92 mS cm−1 using a milling speed of 400 rpm and annealing at 400 °C for 5 hours. When incorporated into a Li4Ti5O12-based all-solid-state battery, this electrolyte demonstrates stable cycling performance across varying temperatures. [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]

• A polymer electrolyte was prepared with ultrahigh dielectric constant. • Better interfacial properties with lithium metal electrodes in symmetric batterys. • A simple and total solvent-free preparation process of solid-state electrolytes. Developing Li-metal batteries (LMBs) requires stability and uniform deposition of lithium during operation. However, lithium dendrites and the extremely low conductivity of the quasi-solid polymer electrolyte (qSPE) limit their performance. A high-throughput screen has been carried out here with the assistance of artificial intelligence (AI) to find a promising electrolyte material – Lithium stearate, which is first used to prepare and form qSPE. The qSPE is named as lithium stearate electrolyte (LST) possessing high Li+ ionic transference number (0.67) and conductivity (8.08 × 10−4 S cm−1) at 25 °C, which is attributed to the lithium stearate interweaving and poly(tetrafluoroethylene) (PTFE) fibrilization. Furthermore, the ultrahigh dielectric properties (ε = 792 @ 100 Hz) of LST fixed the anti-ion pair, (stable anion) minimized the space charge region on the surface of the anode. At the same time, the higher LUMO value of LST inhibits the Li-dendrite growth effectively. The excellent properties of quasi-solid polymer electrolytes make them suitable to be used in solid LMBs. [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]

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 lithium argyrodites with ultrahigh ionic conductivity show great potential as solid electrolytes in all-solid-state batteries, while the poor moisture and lithium metal compatibility limit their applications. Here, by tailoring Sb and O dual dopant, Li 5.5 P 0.96 Sb 0.04 S 4.40 O 0.10 Cl 1.5 electrolyte delivers a high Li-ion conductivity up to 7.20 mS cm−1, excellent air/moisture and lithium metal endurance. The improved air stability is due to the strong Sb–S and P–O bonds in the co-doped electrolyte, inhibiting the reaction with water. While the enhanced lithium metal stability is attributed to the formation of the Li–Sb alloy layer, impeding the growth of lithium dendrites during cycling. The lithium symmetric cell using Li 5.5 P 0.96 Sb 0.04 S 4.40 O 0.10 Cl 1.5 exhibits high critical current density (1.5 mA cm−2) and ultralong cyclability (750 h, 0.1 mA cm−2). The all-solid-state lithium metal battery using LiNi 0.6 Mn 0.2 Co 0.2 O 2 cathode affords a high initial discharge capacity of 144.2 mAh g−1 at 0.1C. Moreover, the assembled battery shows a discharge capacity of 116.2 mAh g−1 at 0.5C and a capacity retention rate of 83.2% after 200 cycles. This work provides the guideline to design sulfide solid electrolytes that enable all-solid-state lithium metal batteries with high energy density and long cyclability. [Display omitted] • Sb–O-doped lithium argyrodite affords a high ionic conductivity of 7.2 mS cm−1. • The Sb–O dual-doping leads to improved air/moisture stability. • Solid-state lithium metal battery retains 83.5% capacity after 200 cycles at 0.5C. [ABSTRACT FROM AUTHOR]

The coating layer can effectively mitigate the undesirable side effects that occur at the active material/sulfide electrolyte interface in the cathode mixture. Plenty of research has reported the coating layer effect in the typical voltage window, while the influence at different voltage windows is unclear. Herein, the degradation mechanism of the bare and LiNbO 3 coated LiCoO 2 electrodes in all-solid-state batteries when cycled at different cut-off voltages has been systematically investigated. Thecoated electrodes exhibit superior electrochemical performance than the bare electrodes at different charging/discharging rates when the upper cut-off voltage is 3.6 V, while both electrodes show fast degradation of battery performance at higher cut-off voltages (3.9 and 4.2 V). The electrochemical performances are highly dependent on the interfacial stability between the active material and solid electrolyte in the cathode mixture and the structural instability of LiCoO 2 at different voltage windows. The evolution of interfacial resistances is systematically investigated in combination of in-situ EIS, relaxation time distribution (DRT), TEM, and XPS. Structural changes of bare and coated LiCoO 2 before and after cycled at different cut-off voltages are studied by XRD, TEM, and dQ/dV analysis. The clarification of complex interfaces and phase stability evolution of LiCoO 2 provides a strong theoretical basis for constructing high-performance all-solid-state batteries. The coating strategy can slow down the volume change of electrode materials and ensure the stability of electrolytes to construct a good solid-state contact. Exploring the difference and applicability of coating strategy under the external conditions of high voltage is crucial for the construction of solid-state batteries with high energy density and long cycles. [Display omitted] [ABSTRACT FROM AUTHOR]

Engineering high conductive Li 7 P 2 S 8 I via Cl- doping for all-solid-state Li-S batteries workable at different operating temperatures. [Display omitted] • The electrolyte Li 7 P 2 S 8 I 0.5 Cl 0.5 achieves a high ionic conductivity of 3.08 mS/cm via Cl doping. • 3Li 2 S-LiI/Li 7 P 2 S 8 I 0.5 Cl 0.5 /Li-In battery delivers excellent capacity and rate performances at different temperatures. • The capacity contribution of the Li 7 P 2 S 8 I 0.5 Cl 0.5 electrolyte in cathode mixture are unraveled. • HP-Li 7 P 2 S 8 I 0.5 Cl 0.5 possesses an enhanced ionic conductivity of 6.67 mS/cm and outstanding stability against lithium. High ionic conductivity and excellent lithium compatibility for sulfide solid electrolytes are vital to developing solid-state Li-metal batteries with high energy density and safety. Li 7 P 2 S 8 I has attracted significant attention due to its low cost, good stability towards lithium metal, and low annealing temperature. However, the low conductivity compared to liquid electrolyte and poor stability with Li metal at high current density limits its applications in solid-state batteries. In this work, the conductivity of Li 7 P 2 S 8 I is first increased from 1.53 mS/cm to 3.08 mS/cm by Cl- doping. The enhanced ionic conductivity is due to the introduction of S2-/Cl-/I- disorder structure in the structure. Then, the Li-ion conductivity of Li 7 P 2 S 8 I 0.5 Cl 0.5 is enhanced up to 6.67 mS/cm via optimizing the pellet-making pressures and temperatures with the hot-press technique. Because of the superior conductivity, the assembled Li 2 S-LiI/Li 7 P 2 S 8 I 0.5 Cl 0.5 /Li-In battery delivers initial discharge capacities of 1051.0 mAh/g, 1385.0 mAh/g, and 713 mAh/g under 0.13 mAh/cm2 at room temperature, 60 °C, and 0 °C, respectively. Moreover, the capacity contribution of the Li 7 P 2 S 8 I 0.5 Cl 0.5 electrolyte in cathode mixture are unraveled, which shows reversible charge/discharge more than 80 cycles and confirms the extra capacity from the electrolytes in the cathode mixture. The hot-press Li 7 P 2 S 8 I 0.5 Cl 0.5 pellet shows excellent lithium compatibility and dendrite suppression capability, achieving stable lithium plating/stripping up to 280 h at 0.1 mA/cm2. The corresponding 3Li 2 S-LiI/Li 7 P 2 S 8 I 0.5 Cl 0.5 /Li battery delivers an initial discharge capacity of 474 mAh/g at 0.13 mA/cm2 and capacity retention of 83% after 30 cycles. This work provides a promising strategy to explore sulfide electrolytes enabling solid-state Li-Metal battery. [ABSTRACT FROM AUTHOR]

Li 6 PS 5 I electrolyte shows significant potential as solid electrolytes due to its low cost and high stability. However, the poor room temperature Li-ion conductivity (10−6 S/cm) limits its applications in solid-state batteries. This work aims to increase the conductivity of Li 6 PS 5 I by introducing LiCl in the structure using high-rotation mechanical milling. Structure analysis confirms that a minor dopant of Cl− can form a single-phase of Li 6 PS 5 Cl x I 1-x argyrodite electrolytes, while a large doping amount yields a mixture of the Li 6 PS 5 I and Li 6 PS 5 Cl phases. The modified electrolytes with "composition" Li 6 PS 5 Cl 0.7 I 0.3 show the highest room temperature Li-ion conductivity among the milled and sintered sample, 7.37 × 10−4 and 2.33 × 10−3 S/cm, both of which are much higher than the conductivity of pristine Li 6 PS 5 I. Solid-state batteries using the above solid electrolytes combined with LiNbO 3 -coated LiNi 0.7 Mn 0.2 Co 0.1 O 2 cathode and Li In anode display excellent electrochemical performances. The battery using annealed Li 6 PS 5 Cl 0.7 I 0.3 electrolyte delivers improved discharge capacities and extended cycling performances at different operating temperatures. This work provides an effective strategy to design high conductivity Li 6 PS 5 I-based solid electrolytes for solid-state batteries. • LiCl promote the Li-ion conductivity of Li 6 PS 5 I electrolytes. • Solid-state battery using Li 6 PS 5 Cl 0.7 I 0.3 electrolyte shows high capacity and good cycling performance. • In-situ EIS reveals the resistance evolution of solid-state batteries using Li 6 PS 5 Cl 0.7 I 0.3 electrolytes. [ABSTRACT FROM AUTHOR]

Large-scale applications of Li 6 PS 5 I electrolytes have been limited due to their low ionic conductivities. This work demonstrated the conductivity enhancement of Li 6 PS 5 I via introducing more iodine in the structure. Li 5.5 PS 4.5 I 1.5 electrolyte synthesized by the mechanical milling route exhibits high ionic conductivity of 0.31 mS/cm at room temperature, which is double times higher than the pristine material. Symmetric cell and half-cell tests confirm that Li 5.5 PS 4.5 I 1.5 suffers from poor chemical/electrochemical stability towards the high-voltage cathode and high activation energy for lithium-ions transport in cathode/electrolyte interface. The introduction of Li 3 InCl 6 ionic additive in the cathode can improve compatibility with LiNi 0.7 Co 0.1 Mn 0.2 O 2 cathode, yielding better electrochemical performances. Li 5.5 PS 4.5 I 1.5 -based solid-state battery using Se 0.05 S 0.95 @pPAN displays a high initial discharge capacity and a capacity of 728 mAh/g after 30 cycles. This work provides a new route to explore iodine-based solid electrolytes with higher ionic conductivity for solid-state batteries. [Display omitted] [ABSTRACT FROM AUTHOR]

• A facile process is developed to prepare argyrodite electrolytes in large quantities. • The electrolyte Li 5.5 PS 4.5 Cl 1.5 achieves a high ionic conductivity of 9.03 mS/cm. • The SSBs deliver superior rate capability and cycling performance at RT and −20 ℃. Solid-state batteries (SSBs) employing sulfide electrolytes (SEs) are considered with poor rate capability and short cycling span life, especially towards the pristine nickel-rich cathode. The high cost, low conductivity, and compatibility are regarded as the major obstacles. In this work, chlorine-rich Li 5.5 PS 4.5 Cl 1.5 electrolyte with high conductivity (9.03 mS/cm) is synthesized via an easy scale-up route. The role of carbon in the cathode mixture is unraveled at room temperature (RT) and low temperature. SSBs using designed cathode without carbon deliver capacity retention of 82.4% after 10,000 cycles under 10C at room temperature and 97.0% after 200 cycles under 0.2C at −20 ℃. This research shows the potential of utilizing SEs to manufacture SSBs with high rates and long cyclability under different temperatures. [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]