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Compared to traditional lithium‐ion batteries with liquid electrolytes, all‐solid‐state lithium batteries have attracted extensive attention due to their heightened safety and energy density. Lithium argyrodite materials are promising solid electrolytes (SE) due to their high ionic conductivity, low grain boundary resistance, and favorable mechanical properties. However, the poor chemical/electrochemical stability of lithium argyrodite electrolytes toward the bare lithium metal anode inhibits their applications in all‐solid‐state lithium metal batteries (ASSLMBs). Here, Li‐SnF2 composite anodeswas used to induce the formation of solid electrolyte interphase (SEI) composed of LiCl, LiF, and Li22Sn5 at the Li/SE interface. The high interface energy barriers for LiF and LiCl induces the uniform deposition of lithium ions, thus hindering the growth of lithium dendrites. Meanwhile, the fast Li‐ion diffusion coefficient of the Li22Sn5 alloy accelerates Li‐ion migration across the interface section. The symmetrical cell exhibits stable cycling performance over long durations over 300 h at 0.5 mA cm−2. Moreover, the LiNbO3@NCM712/Li5.5PS4.5Cl1.5/Li‐10%SnF2 battery delivers a high initial discharge capacity of 170.9 mAh g−1 at 0.1C and retains 72.9% of its original capacity after 500 cycles at 0.5C. The facial approach for Li‐SnF2 composite anode enables the production of ASSLMBs with superior electrochemical performance. [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 sufficient and reversible active lithium is the cornerstone for the operation of high‐energy lithium‐ion batteries. However, active lithium is inevitably depleted due to the formation of a solid electrolyte and the presence of irreversible side reactions. The shortage of lithium in optimally designed batteries not only leads to a depreciation of energy density but also deteriorates the electrode structure resulting in degradation of cycle life. Inspiringly, prelithiation technology that additionally compensates for lithium has been proposed and is playing an increasingly significant role in enhancing battery energy density and prolonging cycle life. Herein, guided by the factors that initiate lithium loss, the action mechanism and the effectiveness of prelithiation are scrutinized. Moreover, the emerging advanced prelithiation technologies based on anode/cathode materials, the key barriers, and the applicability at scale are systematically summarized and compared. Integrating the challenges and development trends aspires to provide a comprehensive prelithiated hybrid lithium replenishment and storage technology as a reference in the scale‐up of prelithiation technologies. [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]

High‐energy density and ultra‐long cycling lifespan are of great significance in pursuit of practical lithium–sulfur (Li‐S) batteries, in which the construction of ultrathick, high‐areal‐capacity, and stable‐cycling sulfur cathodes remains challenging. Here, a unique layered reinforced concrete structure (LRCS) is reported by integrating an ice‐template method with incorporating carbon fibers in the thick electrodes for Li‐S batteries. The LRCS enables aligned through‐channel structure and intertwined conductive network, which lead to both fast kinetics of ions/electrons transport and strengthened electrode integrity to tolerate the volume change during cycling and the dimensional deformation under a high compaction density. Benefiting from the unique structure, the ultra‐thick Se0.05S0.95 @ pPAN cathode (20.2 mg cm−2) delivers a high capacity of 10 mAh cm−2 and excellent capacity retention of 80.8% over 140 cycles at a low electrolyte‐to‐sulfur ratio of 2 and a negative‐to‐positive capacity ratio of 2.7, corresponding to a calculated energy density of 390 Wh kg−1. This investigation not only provides guidance for the design of thick sulfur electrodes but also paves the way for the development of practical Li‐S batteries. [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]

Chlorine-rich argyrodite Li 5.5 PS 4.5 Cl 1.5 with low-cost and high ionic conductivity displays great potential as a solid electrolyte for solid-state battery. However, poor compatibility with bare high-voltage cathode limits its applications. Here, the Li 2 ZrO 3 coating and Li 3 InCl 6 isolating layer strategy are employed to mitigate the interfacial instability between Li 5.5 PS 4.5 Cl 1.5 electrolytes and LiNi 0.7 Co 0.1 Mn 0.2 O 2 materials, respectively. A diversified combination of two strategies is applied to construct all-solid-state batteries with a long lifespan and high energy density. Electrochemical performance results indicate that introducing Li 3 InCl 6 electrolyte in the cathode mixture yields high discharge capacities at beginning and then suffers rapid capacity degradation during extended cycling. In contrast, the assembled Li 2 ZrO 3 @LiNi 0.7 Co 0.1 Mn 0.2 O 2 /Li 5.5 PS 4.5 Cl 1.5 /Li–In battery delivers slightly lower capacities and superior capacity retention. Multiple characterization methods are employed to unravel the mechanism behind battery performance differences. The poor cycle performance of Li 3 InCl 6 -involved solid-state battery configurations is partially associated with the decomposition of Li 3 InCl 6 in the cathode mixture. The Li 2 ZrO 3 coating layer mitigates the side reaction between LiNi 0.7 Co 0.1 Mn 0.2 O 2 and Li 3 InCl 6 , resulting in enhanced capacities and improved cyclability. Furthermore, the interfacial instability between Li 3 InCl 6 and Li 5.5 PS 4.5 Cl 1.5 electrolytes leads to the poor cycling performance of batteries containing the Li 3 InCl 6 /Li 5.5 PS 4.5 Cl 1.5 bilayer structure. This work offers a comprehensive guide for designing high-performances all-solid-state lithium batteries. • Li 2 ZrO 3 coating layer is introduced to alleviate instability of cathode interface. • Li 3 InCl 6 separator layer is utilized to isolate cathode and Li 5.5 PS 4.5 Cl 1.5. • The advantages of Li 2 ZrO 3 and Li 3 InCl 6 protecting strategies have been studied. • Two protection strategies are combined to improve battery performance. • The instability between Li 3 InCl 6 and Li 5.5 PS 4.5 Cl 1.5 affects battery performance. [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]

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]

A free-standing flexible Co-MOF/MXene hybrid film was prepared by inserting 2D Co-MOF nanosheets between MXene layers based on layer upon layer self-assembly strategy. Li-O 2 batteries based on Co-MOF/MXene film as cathode have ultra-high capacity, excellent cycle stability and excellent rate performance. [Display omitted] • A free-standing flexible hybird film was prepared as cathode for Li-O 2 batteries. • The Co-MOF/MXene hybrid film has high ORR catalytic activity. • The interlayer spacing of MXene can be regulated by 2D Co-MOF. • The performance of Li-O 2 batteries can be controlled. Lithium-oxygen (Li-O 2) batteries are considered as a new revolutionary energy storage technology due to their ultra-high theoretical energy density, but many problems of cathode restrict their further development. Here, we prepared a free-standing flexible Co-MOF/MXene hybird film for efficient Oxygen reduction reaction (ORR) and as cathode for Li-O 2 batteries by inserting 2D Co-MOF nanosheets between MXene layers based on electrostatic self-assembly strategy. The Co-MOF/MXene hybrid film with two-dimensional lamellar structure had high ORR catalytic activity, can provide faster Li+ or O 2 expansion channels, promotes the deposition and decomposition of Li 2 O 2 , and it also breaks through the traditional concept of slurry method to prepare cathode of Li-O 2 batteries. Li-O 2 batteries based on Co-MOF/MXene hybird film as cathode had ultra-high capacity (34763 mAh/g at current density of 1000 mA/g), excellent cycle stability (278 cycles, limited capacity of 1000 mAh/g at current density of 1000 mA/g), and outstanding rate performance. Besides, the capacity and cycle performance of Li-O 2 batteries can be controlled by adjusting the loading of 2D Co-MOF and the thickness of Co-MOF/MXene hybrid film. The promising results provide insights the construction of air cathode structure for metal-air batteries, the design of efficient catalyst, and greatly expanded the scope of future research. [ABSTRACT FROM AUTHOR]

Thickening electrodes can significantly increase the energy density and reduce the cost of batteries. However, the electrochemical performance of thick electrodes is limited by the kinetics of lithium-ion transport, resulting in severe polarization and poor electrochemical performance. Here, we investigate the electrochemical behavior of low-tortuous thick electrodes constructed by freeze-drying method. It is shown that low tortuosity can accelerate the transport of lithium-ions and mainly reduce the concentration polarization, leading to improved rate capability. Due to the fast lithium-ions transport kinetics, the electrochemical performance of low tortuous thick electrode is not dominantly determined by concentration polarization until a thickness of 125 μm, much higher than a thickness of 46 μm for the high tortuosity electrode. Thick electrodes with low tortuosity possess a stable cathode electrolyte interface, leading to superior cyclability. Area capacities of low tortuous thick electrodes increase linearly with active material loadings, indicating the independence of specific capacity and electrode thickness. Even at an ultrahigh area loading of 99.56 mg cm−2, this low-tortuous thick electrode delivers an area capacity of 14.8 mAh cm−2. This work reveals the electrochemical behavior of low tortuous thick electrode, providing guidance for applicable thick electrodes in high-performance lithium batteries. The low-tortuous thick electrode with straight lithium-ion transport channels is prepared by freezing drying strategy. Low-tortuous electrodes can not only accelerate lithium-ion transport kinetics and reduce the concentration polarization, but also possess a stable cathode electrolyte interface, enabling superior rate capability and cyclability. The rate determining step of the low-tortuous electrode changes to concentration polarization at bigger critical thickness. [Display omitted] • The low tortuous LiFePO 4 thick electrode was prepared by the freeze-drying route. • Low tortuous electrode structure is beneficial for the transport of lithium-ions. • Low tortuous LiFePO 4 electrode shows superior rate capability and cyclability. [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]

Lithium metal batteries (LMBs) have been regarded as the most promising battery system for the next-generation high energy density batteries due to the extremely high specific capacity of the lithium (Li) metal anode. Unfortunately, the commercial application has been hindered by sharp dendrite Li growth and infinite relative volume change during the repeated charge/discharge process, which lead to severe safety issues and poor cyclability of the battery. Herein, a novel composite Lithium anode is fabricated via thermally infusion molten Li into three-dimensional (3D) nickel foam (NF) framework decorated by lithiophilic Co 3 O 4 nanosheet arrays. The universalized growth of Co 3 O 4 nanosheet on the Ni foam can provide superior wettability between the molten Li and Ni foam, and facilitate more convenient infusion process (5 s). Benefitting from uniform distribution of Li in the 3D host and homogeneous Li+ flux on the surface of the electrode, excellent Li stripping/plating performance (1000 h at 3 mA cm−2 and 275 h at 5 mA cm−2) and dendrite-suppressed morphology are achieved for the Li–Co 3 O 4 /NF composite anode. When utilized in full cells paired with a LiFePO 4 cathode, the Li–Co 3 O 4 /NF composite anode demonstrates greater cyclability and rate performance than bare Li anode. As a result, the obtained Co 3 O 4 /NF demonstrates excellent electrochemical performance as a lithium host skeleton for advanced Li metal battery. Image 1 • The Co 3 O 4 nanosheet coated on the Ni foam greatly improves the lithiophilicity of the Ni foam framework and enables faster Li-infusion process of less than 5s. • This Li–Co 3 O 4 /NF composite anode displays excellent electrochemical performance in symmetrical cell and exhibits a much stable overpotential, and maintains flat voltage profiles over 1000 h at a current density of 3 mA cm−2. • This Li–Co 3 O 4 /NF composite anode shows dendrite-free morphology when cycled after 540 cycles at a current density of 5 mA cm−2. • This Li–Co 3 O 4 /NF anodes display superior rate performance and cycling stability with 90% capacity retention after 500 cycles at 2C. [ABSTRACT FROM AUTHOR]