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Inorganic superionic conductors possess high ionic conductivity and excellent thermal stability but their poor interfacial compatibility with lithium metal electrodes precludes application in all-solid-state lithium metal batteries1,2. Here we report a LaCl3-based lithium superionic conductor possessing excellent interfacial compatibility with lithium metal electrodes. In contrast to a Li3MCl6 (M = Y, In, Sc and Ho) electrolyte lattice3-6, the UCl3-type LaCl3 lattice has large, one-dimensional channels for rapid Li+ conduction, interconnected by La vacancies via Ta doping and resulting in a three-dimensional Li+ migration network. The optimized Li0.388Ta0.238La0.475Cl3 electrolyte exhibits Li+ conductivity of 3.02 mS cm-1 at 30 °C and a low activation energy of 0.197 eV. It also generates a gradient interfacial passivation layer to stabilize the Li metal electrode for long-term cycling of a Li-Li symmetric cell (1 mAh cm-2) for more than 5,000 h. When directly coupled with an uncoated LiNi0.5Co0.2Mn0.3O2 cathode and bare Li metal anode, the Li0.388Ta0.238La0.475Cl3 electrolyte enables a solid battery to run for more than 100 cycles with a cutoff voltage of 4.35 V and areal capacity of more than 1 mAh cm-2. We also demonstrate rapid Li+ conduction in lanthanide metal chlorides (LnCl3; Ln = La, Ce, Nd, Sm and Gd), suggesting that the LnCl3 solid electrolyte system could provide further developments in conductivity and utility.
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Metallic Zn is considered as a promising anode material because of its abundance, eco-friendliness, and high theoretical capacity. However, the uncontrolled dendrite growth and side reactions restrict its further practical application. Herein, we proposed a ß-cyclodextrin-modified multiwalled carbon nanotube (CD-MWCNT) layer for Zn metal anodes. The obtained CD-MWCNT layer with high affinity to Zn can significantly reduce the transfer barrier of Zn2+ at the electrode/electrolyte interface, facilitating the uniform deposition of Zn2+ and suppressing water-caused side reactions. Consequently, the Zn||Zn symmetric cell assembled with CD-MWCNT shows a significantly enhanced cycling durability, maintaining a cycling life exceeding 1000 h even under a high current density of 5 mA cm-2. Furthermore, the full battery equipped with a V2O5 cathode displays an unparalleled long life. This work unveils a promising avenue toward the achievement of high-performance Zn metal anodes.
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Lithium-sulfur (Li-S) batteries are expected to be the next-generation energy storage system due to the ultrahigh theoretical energy density and low cost. However, the notorious shuttle effect of higher-order polysulfides and the uncontrollable lithium dendrite growth are the two biggest challenges for commercially viable Li-S batteries. Herein, these two main challenges are solved by in situ polymerization of bi-functional gel polymer electrolyte (GPE). The initiator (SiCl4) not only drives the polymerization of 1,3-dioxolane (DOL) but also induces the construction of a hybrid solid electrolyte interphase (SEI) with inorganic-rich compositions on the Li anode. In addition, diatomaceous earth (DE) is added and anchored in the GPE to obtain PDOL-SiCl4-DE electrolyte through in situ polymerization. Combined with density functional theory (DFT) calculations, the hybrid SEI provides abundant adsorption sites for the deposition of Li+, inhibiting the growth of lithium dendrites. Meanwhile, the shuttle effect is greatly alleviated due to the strong adsorption capacity of DE toward lithium polysulfides. Therefore, the Li/Li symmetric cell and Li-S full cell assembled with PDOL-SiCl4-DE exhibit excellent cycling stability. This study offers a valuable reference for the development of high performance and safe Li-S batteries.
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The challenge of constructing a mechanically robust yet lightweight artificial solid-electrolyte interphase layer on lithium (Li) anodes highlights a trade-off between high battery safety and high energy density. Inspired by the intricate microstructure of the white sea urchin, we first develop a polyvinyl fluoride-hexafluoropropylene (PVDF-HFP) interfacial layer with a triple periodic minimal surface structure (TPMS) that could offer maximal modulus with minimal weight. This design endows high mechanical strength to an ordered porous structure, effectively reduces local current density, polarization, and internal resistance, and stabilizes the anode interface. At a low N/P ratio of ~3, using LiFePO4 as the cathode, Li anodes protected by TPMS-structured PVDF-HFP achieve an extremely low capacity-fading-rate of approximately 0.002 % per cycle over 200 cycles at 1â C, with an average discharge capacity of 142â mAh g-1. Meanwhile, the TPMS porous structure saves 50â wt % of the interfacial layer mass, thereby enhancing the energy density of the battery. The TPMS structure is conducive to large-scale additive manufacturing, which will provide a reference for the future development of lightweight, high-energy-density secondary batteries.
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Solid electrolytes (SEs) are central components that enable high-performance, all-solid-state lithium batteries (ASSLBs). Amorphous SEs hold great potential for ASSLBs because their grain-boundary-free characteristics facilitate intact solid-solid contact and uniform Li-ion conduction for high-performance cathodes. However, amorphous oxide SEs with limited ionic conductivities and glassy sulfide SEs with narrow electrochemical windows cannot sustain high-nickel cathodes. Herein, we report a class of amorphous Li-Ta-Cl-based chloride SEs possessing high Li-ion conductivity (up to 7.16 mS cm-1) and low Young's modulus (approximately 3 GPa) to enable excellent Li-ion conduction and intact physical contact among rigid components in ASSLBs. We reveal that the amorphous Li-Ta-Cl matrix is composed of LiCl43-, LiCl54-, LiCl65- polyhedra, and TaCl6- octahedra via machine-learning simulation, solid-state 7Li nuclear magnetic resonance, and X-ray absorption analysis. Attractively, our amorphous chloride SEs exhibit excellent compatibility with high-nickel cathodes. We demonstrate that ASSLBs comprising amorphous chloride SEs and high-nickel single-crystal cathodes (LiNi0.88Co0.07Mn0.05O2) exhibit â¼99% capacity retention after 800 cycles at â¼3 C under 1 mA h cm-2 and â¼80% capacity retention after 75 cycles at 0.2 C under a high areal capacity of 5 mA h cm-2. Most importantly, a stable operation of up to 9800 cycles with a capacity retention of â¼77% at a high rate of 3.4 C can be achieved in a freezing environment of -10 °C. Our amorphous chloride SEs will pave the way to realize high-performance high-nickel cathodes for high-energy-density ASSLBs.
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Aqueous rechargeable zinc-based batteries (ZBBs) are emerging as desirable energy storage systems because of their high capacity, low cost, and inherent safety. However, the further application of ZBBs still faces many challenges, such as the issues of uncontrolled dendrite growth and severe parasitic reactions occurring at the Zn anode. Herein, an amino-grafted bacterial cellulose (NBC) film is prepared as artificial solid electrolyte interphase (SEI) for the Zn metal anodes, which can significantly reduce zinc nucleation overpotential and lead to the dendrite-free deposition of Zn metal along the (002) crystal plane more easily without any external stimulus. More importantly, the chelation between the modified amino groups and zinc ions can promote the formation of an ultra-even amorphous SEI upon cycling, reducing the activity of hydrate ions, and inhibiting the water-induced side reactions. As a result, the Zn||Zn symmetric cell with NBC film exhibits lower overpotential and higher cyclic stability. When coupled with the V2 O5 cathode, the practical pouch cell achieves superior electrochemical performance over 1000 cycles.
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In consideration of high specific capacity and low redox potential, lithium metal anodes have attracted extensive attention. However, the cycling performance of lithium metal batteries generally deteriorates significantly under the stringent conditions of high temperature due to inferior heat tolerance of the solid electrolyte interphase (SEI). Herein, controllable SEI nanostructures with excellent thermal stability are established by the (trifluoromethyl)trimethylsilane (TMSCF3 )-induced interface engineering. First, the TMSCF3 regulates the electrolyte decomposition, thus generating an SEI with a large amount of LiF, Li3 N, and Li2 S nanocrystals incorporated. More importantly, the uniform distributed nanocrystals have endowed the SEI with enhanced thermostability according to the density functional theory simulations. Particularly, the sub-angstrom visualization on SEI through a conventional transmission electron microscope (TEM) is realized for the first time and the enhanced tolerance to the heat damage originating from TEM imaging demonstrates the ultrahigh thermostability of SEI. As a result, the highly thermostable interphase facilitates a substantially prolonged lifespan of full cells at a high temperature of 70 °C. As such, this work might inspire the universal interphase design for high-energy alkali-metal-based batteries applicated in a high-temperature environment.
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Sodium (Na) metal is able to directly use as a battery anode but have a highly reductive ability of unavoidably occurring side reactions with organic electrolytes, resulting in interfacial instability as a primary factor in performance decay. Therefore, building stable Na metal anode is of utmost significance for both identifying the electrochemical performance of laboratory half-cells employed for quantifying samples and securing the success of room-temperature Na metal batteries. In this work, we propose an NaF-rich interface rapidly prepared by pressure and diglyme-induced defluorination reaction for stable Na metal anode. Once the electrolyte is dropped into the coin-type cells followed by a slight squeeze, the Na metal surface immediately forms a protective layer consisting of amorphous carbon and NaF, effectively inhibiting the dendrite growth and dead Na. The resultant Na metal anode exhibits a long-term cycling lifespan over 1800 h even under the area capacity of 3.0 mAh cm-2 . Furthermore, such a universal and facile method is readily applied in daily battery assembly regarding Na metal anode.
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Lithium-rich layered oxide (LRLO) materials have attracted significant attention due to their high specific capacity, low cost, and environmental friendliness. However, owing to its unique capacity activation mechanism, the release of lattice oxygen during the first charge process leads to a series of problems, such as severe voltage decay, poor cycle stability, and poor rate performance. Herein, a fluorinated quasi-solid-state electrolyte (QSSE) via a simple thermal polymerization method toward lithium metal batteries with LRLO materials is reported. The well-designed QSSE exhibits an ionic conductivity of 6.4 × 10-4 S cm-1 at 30 °C and a wide electrochemical stable window up to 5.6 V. Most importantly, XPS spectra demonstrate the generation of a LiF-rich electrode-electrolyte interface (EEI), where the in situ generated LiF provides strong protection against the structural degradation of LRLO materials and directs the uniform plating/stripping behaviors of lithium-ions to inhibit the formation of lithium dendrites. As a result, LRLO/QSSE/Li batteries exhibit excellent rate performance and demonstrate a large initial capacity for 209.7 mA h g-1 with a capacity retention of 80.8% after 200 cycles at 0.5C. This work provides a new insight for the LiF-rich EEI design of safe, high-performance quasi-solid-state lithium metal batteries.
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The use of poly(1,3-dioxolane) (PDOL) electrolyte for lithium batteries has gained attention due to its high ionic conductivity, low cost, and potential for large-scale applications. However, its compatibility with Li metal needs improvement to build a stable solid electrolyte interface (SEI) toward metallic Li anode for practical lithium batteries. To address this concern, this study utilized a simple InCl3 -driven strategy for polymerizing DOL and building a stable LiF/LiCl/LiIn hybrid SEI, confirmed through X-ray photoelectron spectroscopy (XPS) and cryogenic-transmission electron microscopy (Cryo-TEM). Furthermore, density functional theory (DFT) calculations and finite element simulation (FES) verify that the hybrid SEI exhibits not only excellent electron insulating properties but also fast transport properties of Li+ . Moreover, the interfacial electric field shows an even potential distribution and larger Li+ flux, resulting in uniform dendrite-free Li deposition. The use of the LiF/LiCl/LiIn hybrid SEI in Li/Li symmetric batteries shows steady cycling for 2000 h, without experiencing a short circuit. The hybrid SEI also provided excellent rate performance and outstanding cycling stability in LiFePO4 /Li batteries, with a high specific capacity of 123.5 mAh g-1 at 10 C rate. This study contributes to the design of high-performance solid lithium metal batteries utilizing PDOL electrolytes.
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Several isostructural lanthanide metal-organic frameworks, viz. [Ln(DCHB)1.5phen]n (Ln-MOFs, where Ln = Eu for 1, Tb for 2, Sm for 3 and Dy for 4), are successfully synthesized through the hydrothermal reactions of 4'-di(4-carboxylphenoxy)hydroxyl-2, 2'-bipyridyl (H2DCHB) and lanthanide nitrates as well as chelator 1,10-phenantroline (phen). These structures are characterized by single-crystal X-ray diffraction, and the representative Ln-MOF 1 is a fivefold interpenetrated framework with the uncoordinated Lewis base N sites form DCHB2- ligands. The photoluminescence research studies reveal that Ln-MOFs 1-4 exhibit characteristic fluorescent emissions from ligand-induced lanthanide Ln(III) ions, while the single-component emission spectra of Ln-MOF 4 are all located in a white region under different excitations. The absence of coordinated water and the interpenetration property of the structures are conducive to the structure rigidity, and the results display that Ln-MOF 1 has high thermal/chemical stabilities in common solvents and a wide pH range as well as the boiling water. Notably, luminescent sensing studies reveal that Ln-MOF 1 with prominent fluorescence properties can perform in highly sensitive and selective sensing of vanillylmandelic acid (VMA) in aqueous systems (KSV = 562.8 L·mol-1; LOD = 4.6 × 10-4 M), which can potentially establish a detection platform for the diagnosis of pheochromocytoma via multiquenching mechanisms. Moreover, the 1@MMMs sensing membranes comprised of Ln-MOF 1 and a poly(vinylidene fluoride) (PVDF) polymer can also be facilely developed for VMA detection in aqueous media, suggesting the enhanced convenience and efficiency of practical sensing applications.
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The free transport of anions in a Li metal battery can cause multiple issues, including a high anion transference number, space charge, and concentration polarization, eventually leading to uncontrolled dendrite formation and decreased performance. Herein, we report an anion-anchoring nano-CaCO3 (NC) coating derived from eggshell biowaste for stabilizing Li metal anodes. As the adsorption of local TFSI- anions onto the NC adsorbent can undermine the anion concentration gradient and promote rapid Li-ion diffusion, it can effectively inhibit the proliferation of Li dendrites assisted by the NC coating. Consequently, Li/Cu cells with NC@Cu electrode can achieve a high Coulombic efficiency of â¼98.4% for more than 420 cycles and can even reach â¼99.1% at an ultrahigh areal capacity of 20 mAh cm-2. In particular, full cells with NC/Li@Cu electrodes show a stable lifespan of over 240 cycles with an average efficiency of â¼99.8% at a low N/P ratio of â¼3.3.
Asunto(s)
Biomasa , Aniones , Transporte IónicoRESUMEN
The proliferation of lithium (Li) dendrites stemming from uncontrollable Li deposition seriously limits the practical application of Li metal batteries. The regulation of uniform Li deposition is thus a prerequisite for promoting a stable Li metal anode. Herein, a commercial lithiophilic skeleton of soybean protein fiber (SPF) is introduced to homogenize the Li-ion flux and induce the biomimetic Li growth behavior. Especially, the SPF can promote the formation of a LiF-nanocrystal-enriched interface upon cycling, resulting in low interfacial impedance and rapid charge transfer kinetics. Finally, the SPF-mediated Li metal anode can achieve high Coulombic efficiency of 98.7% more than 550 cycles and a long-term lifespan over 3400 h (â¼8500 cycles) in symmetric tests. Furthermore, the practical pouch cell modified with SPF can maintain superior electrochemical performance over 170 cycles under a low N/P ratio and high mass loading of the cathode.
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Suministros de Energía Eléctrica , Litio , Nanopartículas , Proteínas de Soja , Electrodos , Litio/química , Proteínas de Soja/químicaRESUMEN
Sulfide electrolytes promise superior ion conduction in all-solid-state lithium (Li) metal batteries, while suffering harsh hurdles including interior dendrite growth and instability against Li and moist air. A prerequisite for solving such issues is to uncover the nature of the Li/sulfide interface. Herein, air-stable Li4SnS4 (LSS) as a prototypical sulfide electrolyte is selected to visualize the dynamic evolution and failure of the Li/sulfide interface by cryo-electron microscopy. The interfacial parasitic reaction (2Li + 2Li4SnS4 = 5Li2S + Sn2S3) is validated by direct detection of randomly distributed Li2S and Sn2S3 crystals. A bifunctional buffering layer is consequently introduced by self-diffusion of halide into LSS. Both the interface and the grain boundaries in LSS have been stabilized, eliminating the growing path of Li dendrites. The buffering layer enables the durability of Li symmetric cell (1500 h) and high-capacity retention of the LiFePO4 full-cell (95%). This work provides new insights into the hierarchical design of sulfide electrolytes.
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High-voltage lithium metal batteries (LMBs) pose severe challenges for the matching of electrolytes with aggressive electrodes, especially at low temperatures. Here, we report a rational modification of the Li+ solvation structure to extend the voltage and temperature operating ranges of conventional electrolytes. Ion-ion and ion-dipole interactions as well as the electrochemical window of solvents were tailored to improve oxidation stability and de-solvation kinetics of the electrolyte. Meanwhile, robust and elastic B and F-rich interphases are formed on both electrodes. Such optimization enables Li||LiNi0.5 Mn1.5 O4 cells (90.2 % retention after 400 cycles) and Li||LiNi0.6 Co0.2 Mn0.2 O2 (NCM622) cells (74.0 % retention after 200 cycles) to cycle stably at an ultra-high voltage of 4.9â V. Moreover, NCM622 cells deliver a considerable capacity of 143.5â mAh g-1 at -20 °C, showing great potential for practical uses. The proposed strategy sheds light on further optimization for high-voltage LMBs.
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Lithium (Li)-metal batteries are one of the most promising candidates for the next-generation energy storage devices due to their ultrahigh theoretical capacity. The realistic development of a Li metal battery is greatly impeded by the uncontrollable dendrite proliferation upon the chemically active metallic Li. To visualize the micromorphology or even the atomic structure of Li deposits is undoubtedly crucial, while imaging the sensitive Li still faces a huge challenge technically.Cryogenic electron microscopy (cryo-EM), an emerging imagery technology renowned for structural elucidation of biomaterials, is offering increased possibilities for analyzing sensitive battery materials reaching subangstrom resolution. Particularly for revealing metallic Li, cryo-EM exhibits remarkable superiority compared with the conventional electron imaging technique. On the one hand, cryo-EM could prevent the low melting-point Li metal from being damaged by the high electron dose induced thermal effect. On the other hand, the extremely low temperature immensely retards the rate of the side reaction where the Li reacts with the atmosphere or water vapor before the vacuum state. Consequently, the cryo-EM could acquire a high-resolution image of electron-beam sensitive Li in its native state at the nano- or even atomic scale, thus benefiting the fundamental perception and rational design of Li metal anodes.Thus, in this Account, we aim to highlight the significance of cryo-EM in analyzing metallic Li and developing a high-performance Li metal battery. We focus on how highly resolved cryo-EM realizes the breakthrough in detecting the crucial evolution during battery cycling, e.g., lattice ordering of Li, nanostructures of the solid electrolyte interphase (SEI), nucleation sites, and interface between the solid electrolyte and the Li anode. First, we briefly summarize the progress of Li metal imaging by cryo-EM in a timed sequence. In particular, the recent studies from our group are classified in order to systematically delineate the advantages that cryo-transmission electron microscopy (cryo-TEM) addressed on understanding and developing the Li metal battery. Second, the efforts of exhibiting the long-range ordering Li lattice are described to cognize the crystal orientation of both Li dendrites and uniform spheres. Subsequently, the nanostructures of SEI detected by cryo-TEM, maybe the most key information during Li plating/stripping, are systematically summarized. Benefitting from the subangstrom visualization on the newly formed and the particular inactive SEI after long-term cycling, we emphasize cryo-TEM's guidance in designing a robust, highly Li+ conductive, and Li-restoration facilitated SEI. We then propose the strategy of introducing a nucleation-site to enable uniform Li deposition by showing the evidence of Li nucleation atomically monitored through cryo-TEM. Moreover, the series of the work of atomic imagery and corresponding optimization of the interfaces between the polymer-based solid electrolyte and the Li anode are concluded. Finally, critical perspectives about the further step of cryo-TEM in the realistic development of high-energy density battery systems are also succinctly reviewed.
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Supercooled liquid sulfur microdroplets were directly generated from polysulfide electrochemical oxidation on various metal-containing electrodes. The sulfur droplets remain liquid at 155 °C below sulfur's melting point (Tm = 115 °C), with fractional supercooling change (Tm - Tsc)/Tm larger than 0.40. In operando light microscopy captured the rapid merging and shape relaxation of sulfur droplets, indicating their liquid nature. Micropatterned electrode and electrochemical current allow precise control of the location and size of supercooled microdroplets, respectively. Using this platform, we initiated and observed the rapid solidification of supercooled sulfur microdroplets upon crystalline sulfur touching, which confirms supercooled sulfur's metastability at room temperature. In addition, the formation of liquid sulfur in electrochemical cell enriches lithium-sulfur-electrolyte phase diagram and potentially may create new opportunities for high-energy Li-S batteries.
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Argyrodite Li6 PS5 Cl with high Li+ conductivity is a promising material for solid-state electrolytes (SSEs) in all-solid-state lithium batteries (ASSLBs). However, the narrow electrochemical window of Li6 PS5 Cl limits its applications in ASSLBs with high energy densities, and those that consist of high-voltage cathode materials and metallic lithium anodes. Unstable lithium deposition and stripping at interfaces is also a factor that restricts its industrialization. Herein, the authors investigated the electrochemical stability of Li6 PS5 Cl using it as both the cathode and electrolyte. The Li6 PS5 Cl-C/Li6 PS5 Cl/Li cell and symmetric Li/Li6 PS5 Cl/Li cells failed after a certain number of cycles, and subsequently healed electrochemically. This failure/healing phenomenon recurred during the cycling process. The self-healing behavior is closely related to the electrochemical window, which suggests that it can be controlled by the charge-discharge voltage range. In-depth X-ray photoelectron spectroscopy, in situ Raman spectroscopy, and in situ electrochemical impedance spectroscopy revealed the reversible Li6 PS5 Cl decomposition and metallic lithium growth inside the electrolyte during the cycling process. This self-healing behavior is mainly attributed to the reciprocating lithium growth and reversible redox reaction of the Li6 PS5 Cl decomposition. The proposed self-healing mechanism is a key aspect for sulfide-based SSEs, guiding the interface modification, and material design of ASSLBs.
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High-energy-density lithium (Li) metal batteries suffer from a short lifespan owing to apparently ceaseless inactive Li accumulation, which is accompanied by the consumption of electrolyte and active Li reservoir, seriously deteriorating the cyclability of batteries. Herein, a triiodide/iodide (I3 - /I- ) redox couple initiated by stannic iodide (SnI4 ) is demonstrated to reclaim inactive Li. The reduction of I3 - converts inactive Li into soluble LiI, which then diffuses to the cathode side. The oxidation of LiI by the delithiated cathode transforms cathode into the lithiation state and regenerates I3 - , reclaiming Li ion from inactive Li. The regenerated I3 - engages the further redox reactions. Furthermore, the formation of Sn mitigates the corrosion of I3 - on active Li reservoir sacrificially. In working Li | LiNi0.5 Co0.2 Mn0.3 O2 batteries, the accumulated inactive Li is significantly reclaimed by the reversible I3 - /I- redox couple, improving the lifespan of batteries by twice. This work initiates a creative solution to reclaim inactive Li for prolonging the lifespan of practical Li metal batteries.
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Polysulfide binding and trapping to prevent dissolution into the electrolyte by a variety of materials has been well studied in Li-S batteries. Here we discover that some of those materials can play an important role as an activation catalyst to facilitate oxidation of the discharge product, Li2S, back to the charge product, sulfur. Combining theoretical calculations and experimental design, we select a series of metal sulfides as a model system to identify the key parameters in determining the energy barrier for Li2S oxidation and polysulfide adsorption. We demonstrate that the Li2S decomposition energy barrier is associated with the binding between isolated Li ions and the sulfur in sulfides; this is the main reason that sulfide materials can induce lower overpotential compared with commonly used carbon materials. Fundamental understanding of this reaction process is a crucial step toward rational design and screening of materials to achieve high reversible capacity and long cycle life in Li-S batteries.