Search Results (17)

In this study, we investigate the environmental stability of the sulfide-based argyrodite solid electrolyte Li₆PS₅Cl₀.₅Br₀.₅, a promising candidate for all-solid-state lithium batteries due to its high ionic conductivity and favorable mechanical properties. Despite its potential, the material’s sensitivity to ambient air humidity presents challenges for large-scale battery manufacturing. Moisture exposure leads to performance degradation and the release of toxic hydrogen sulfide (H₂S) gas, raising concerns for workplace safety. The objectives of this study are to validate the electrolyte synthesis process, evaluate the effects of air humidity exposure on its reactivity and ionic conductivity, and establish a standardized protocol for assessing environmental stability. We report a synthesis method based on ball milling and heat treatment that achieves an ionic conductivity of 2.11 mS/cm, along with a fundamental study incorporating modeling and formulation approaches to evaluate the electrolyte’s environmental stability. Furthermore, we introduce a simplified testing method for assessing environmental stability, which may serve as a benchmark protocol for the broader class of argyrodite solid electrolytes. Full article

All-solid-state batteries have garnered significant attention due to their potential to exceed the energy density of conventional lithium-ion batteries, particularly when alloying-based materials or lithium metal anodes are used. However, achieving compatibility with lithium metal remains a persistent bottleneck. In this study, we shed light on the potential of SnHPO₃ tin phosphite and Ni_3.4Sn₄ intermetallic as novel conversion/alloying anode materials for all-solid-state lithium batteries using Li₆PS₅Cl as the solid electrolyte. The two Sn-based active materials were nanostructured by ball-milling to demonstrate considerable promise for application in all-solid-state half-cells. Galvanostatic cycling at room temperature revealed electrochemical behavior based on conversion/alloying reactions akin to those observed in conventional lithium-ion batteries. Promisingly, both materials exhibited satisfying electrochemical stability, with coulombic efficiencies exceeding 97%. These findings indicate that Li₆PS₅Cl solid electrolyte is compatible with Sn-based alloying anodes. Full article

Lithium-titanium-sulfur cathodes have garnered interest due to their distinctive properties and potential applications in lithium-ion batteries. They present various benefits, including lower cost, enhanced safety, and greater energy density compared to the commonly used transition metal oxides. The current trend in lithium-ion batteries is to move to all-solid-state chemistries in order to improve safety and energy density. Several chemistries for solid electrolytes have been studied, tested, and characterized to evaluate the applicability in energy storage system. Among those, sulfur-based Argyrodites have been coupled with cubic rock-salt type Li₂TiS₃ electrodes. In this work, Li₂TiS₃ surfaces were investigated with DFT methods in different conditions, covering the possible configurations that can occur during the cathode usage: pristine, delithiated, and overlithiated. Interfaces were built by coupling selected Li₂TiS₃ surfaces with the most stable Argyrodite surface, as derived from a previous study, allowing us to understand the (electro)chemical compatibility between these two sulfur-based materials. Full article

We introduce a quasi-solid-state electrolyte lithium-sulfur (Li–S) battery (QSSEB) based on a novel Li-argyrodite solid-state electrolyte (SSE), Super P–Sulfur cathode, and Li-anode. The cathode was prepared using a water-based carboxymethyl cellulose (CMC) solution and styrene butadiene rubber (SBR) as the binder while Li₆PS₅F_0.5Cl_0.5 SSE was synthesized using a solvent-based process, via the introduction of LiF into the argyrodite crystal structure, which enhances both the ionic conductivity and interface-stabilizing properties of the SSE. Ionic liquids (IL) were prepared using lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as the salt, with pre-mixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent, and they were used to wet the SSE–electrode interfaces. The effect of IL dilution, the co-solvent amount, the LiTFSI concentration, the C rate at which the batteries are tested and the effect of the introduction of SSE in the cathode, were systematically studied and optimized to develop a QSSEB with higher capacity retention and cyclability. Interfacial reactions occurring at the cathode–SSE interface during cycling were also investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy supported by ab initio molecular dynamics simulations. This work offers a new insight into the intimate interfacial contacts between the SSE and carbon–sulfur cathodes, which are critical for improving the electrochemical performance of quasi-solid-state lithium–sulfur batteries. Full article

Developing argyrodite-type, chlorine-rich, sodium-ion, solid-state electrolytes with high conductivity is a long-term challenge that is crucial for the advancement of all-solid-state batteries (ASSBs). In this study, chlorine-rich, argyrodite-type Na_6−xPS_5−xCl_1+x solid solutions were successfully developed with a solid solution formation range of 0 ≤ x ≤ 0.5. Na_5.5PS_4.5Cl_1.5 (x = 0.5), displaying a highest ionic conductivity of 1.2 × 10⁻³ S/cm at 25 °C, which is more than a hundred times higher than that of Na₆PS₅Cl. Cyclic voltammetry and electrochemical impedance spectroscopy results demonstrated that the rich chlorine significantly enhanced the ionic conductivity and electrochemical stability, in addition to causing a reduction in activation energy. The Na_5.5PS_4.5Cl_1.5 composite also showed the characteristics of a pure ionic conductor without electronic conductivity. Finally, the viability of Na_5.5PS_4.5Cl_1.5 as a sodium electrolyte for all-solid-state sodium batteries was checked in a lab-scale ASSB, showing stable battery performance. This study not only demonstrates new composites of sodium-ionic, solid-state electrolytes with relatively high conductivity but also provides an anion-modulation strategy to enhance the ionic conductivity of argyrodite-type sodium solid-state ionic conductors. Full article

All-solid-state lithium-ion batteries based on solid electrolytes are attractive for electric applications due to their potential high energy density and safety. The sulfide solid electrolyte (e.g., argyrodite) shows a high ionic conductivity (10⁻³ S cm⁻¹). There is an open question related to the sulfide electrode’s fabrication by simply infiltrating methods applied for conventional lithium-ion battery electrodes via homogeneous solid electrolyte solutions, the structure of electrolytes after drying, chemical stability of binders and electrolyte, the surface morphology of electrolyte, and the deepening of the infiltrated electrolyte into the active materials to provide better contact between the active material and electrolyte and favorable lithium ionic conduction. However, due to the high reactivity of sulfide-based solid electrolytes, unwanted side reactions between sulfide electrolytes and polar solvents may occur. In this work, we explore the chemical and electrochemical properties of the argyrodite-based film produced by infiltration mode by combining electrochemical and structural characterizations. Full article

All-solid-state lithium batteries (ASSLBs) using argyrodite electrolyte materials have shown promise for applications in electric vehicles (EVs). However, understanding the effects of processing parameters on the ionic conductivity of these electrolytes is crucial for optimizing battery performance and manufacturing methods. This study investigates the influence of electrolyte operating temperature, electrolyte operating pressure, electrolyte pelletization pressure, and electrolyte pelletizing temperature on the ionic conductivity of the Li₆PS₅Cl_0.5Br_0.5 argyrodite electrolyte (AmpceraTM, D₅₀ = 10 µm). A specially designed test cell is employed for the experimental measurements, allowing for controlled pelletization and testing within the same tooling. The results demonstrate the significant impact of the four parameters on the ionic conductivity of the argyrodite electrolyte. The electrolyte operating temperature has a more pronounced effect than operating pressure, and pelletizing temperature exerts a greater influence than pelletizing pressure. This study provides graphs that aid in understanding the interplay between these parameters and achieving desired conductivity values. It also establishes a baseline for the maximum pelletizing temperature before undesirable degradation of the electrolyte occurs. By manipulating the pelletizing pressure, operating pressure, and pelletizing temperature, battery engineers can achieve the desired conductivity for specific applications. The findings emphasize the need to consider operating conditions to ensure satisfactory low-temperature performance, particularly for EVs. Overall, this study provides valuable insights into processing and operating conditions for ASSLBs utilizing the Li₆PS₅Cl_0.5Br_0.5 argyrodite electrolyte. Full article

Due to the limitations of organic liquid electrolytes, current development is towards high performance all-solid-state lithium batteries (ASSLBs). For high performance ASSLBs, the most crucial is the high ion-conducting solid electrolyte (SE), with a focus on interface analysis between SE and active materials. In the current study, we successfully synthesized the high ion-conductive argyrodite-type (Li₆PS₅Cl) solid electrolyte, which has 4.8 mS cm⁻¹ conductivity at room temperature. Additionally, the present study suggests the quantitative analysis of interfaces in ASSLBs. The measured initial discharge capacity of a single particle confined in a microcavity electrode was 1.05 nAh for LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622)-Li₆PS₅Cl solid electrolyte materials. The initial cycle result shows the irreversible nature of active material due to the formation of the solid electrolyte interphase (SEI) layer on the surface of the active particle; further second and third cycles demonstrate high reversibility and good stability. Furthermore, the electrochemical kinetic parameters were calculated through the Tafel plot analysis. From the Tafel plot, it is seen that asymmetry increases gradually at high discharge currents and depths, which rise asymmetricity due to the increasing of the conduction barrier. However, the electrochemical parameters confirm the increasing conduction barrier with increased charge transfer resistance. Full article

Sulfide-based solid electrolytes exhibit good formability and superior ionic conductivity. However, these electrolytes can react with atmospheric moisture to generate H₂S gas, resulting in performance degradation. In this study, we attempted to improve the stability of the interface between Li metal and an argyrodite Li₆Ps₅Cl solid electrolyte by partially substituting P with Sn to form an Sn–S bond. The solid electrolyte was synthesized via liquid synthesis instead of the conventional mechanical milling method. X-ray diffraction analyses confirmed that solid electrolytes have an argyrodite structure and peak shift occurs as substitution increases. Scanning electron microscopy and energy-dispersive X-ray spectroscopy analyses confirmed that the particle size gradually increased, and the components were evenly distributed. Moreover, electrochemical impedance spectroscopy and DC cycling confirmed that the ionic conductivity decreased slightly but that the cycling behavior was stable for about 500 h at X = 0.05. The amount of H₂S gas generated when the solid electrolyte is exposed to moisture was measured using a gas sensor. Stability against atmospheric moisture was improved. In conclusion, liquid-phase synthesis could be applied for the large-scale production of argyrodite-based ${\mathrm{Li}}_6{\mathrm{PS}}_5\mathrm{Cl}$ solid electrolytes. Moreover, Sn substitution improved the electrochemical stability of the solid electrolyte. Full article

All-solid-state lithium-ion batteries with argyrodite solid electrolytes have been developed to attain high conductivities of 10⁻³ S cm⁻¹ in studies aiming at fast ionic conductivity of electrolytes. However, no matter how high the ionic conductivity of the electrolyte, the design of the cathode composite is often the bottleneck for high performance. Thus, optimization of the composite cathode formulation is of utmost importance. Unfortunately, many reports limit their studies to only a few parameters of the whole electrode formulation. In addition, different measurement setups and testing conditions employed for all-solid-state batteries make a comparison of results from mutually independent studies quite difficult. Therefore, a detailed investigation on different key parameters for preparation of cathodes employed in all-solid-state batteries is presented here. Employing a rational approach for optimization of composite cathodes using solid sulfide electrolytes elucidated the influence of different parameters on the cycling performance. First, powder electrodes made without binders are investigated to optimize several parameters, including the active materials’ particle morphology, the nature and amount of the conductive additive, the particle size of the solid electrolyte, as well as the active material-to-solid electrolyte ratio. Finally, cast electrodes are examined to determine the influence of a binder on cycling performance. Full article

Argyrodite solid electrolytes such as lithium phosphorus sulfur chloride (Li₆PS₅Cl) have recently attracted great attention due to their excellent lithium-ion transport properties, which are applicable to all-solid-state lithium batteries. In this study, we report the improved ionic conductivity of an argyrodite solid electrolyte, Li₆PS₅Cl, in all-solid-state lithium batteries via the co-doping of chlorine (Cl) and aluminum (Al) elements. Electrochemical analysis was conducted on the doped argyrodite structure of Li₆PS₅Cl, which revealed that the substitution of cations and anions greatly improved the ionic conductivity of solid electrolytes. The ionic conductivity of the Cl- and Al-doped Li₆PS₅Cl (Li_5.4Al_0.1PS_4.7Cl_1.3) electrolyte was 7.29 × 10⁻³ S cm⁻¹ at room temperature, which is 4.7 times higher than that of Li₆PS₅Cl. The Arrhenius plot of the Li_5.4Al_0.1PS_4.7Cl_1.3 electrolyte further elucidated its low activation energy at 0.09 eV. Full article

Solid-state argyrodite electrolytes are promising candidate materials to produce safe all-solid-state lithium batteries (ASSLBs) due to their high ionic conductivity. These batteries can be used to power electric vehicles and portable consumer electronics which need high power density. Atomic-scale modeling with ab initio calculations became an invaluable tool to better understand the intrinsic properties and stability of these materials. It is also used to create new structures to tailor their properties. This review article presents some of the recent theoretical investigations based on atomic-scale modeling to study argyrodite electrolytes for ASSLBs. A comparison of the effectiveness of argyrodite materials used for ASSLBs and the underlying advantages and disadvantages of the argyrodite materials are also presented in this article. Full article

Due to their safety and high power density, one of the most promising types of all-solid-state lithium batteries is the one made with the argyrodite solid electrolyte (ASE). Although substantial efforts have been made toward the commercialization of this battery, it is still challenged by some technical issues. One of these issues is to prevent the side reactions at the interface of the ASE and the cathode active material (CAM). A solution to address this issue is to coat the CAM particles with a material that is compatible with both ASE and CAM. Prior studies show that the lithium niobate, LiNbO₃, (LNO) is a promising material for coating CAM particles to reduce the interfacial side reactions. However, no systematic study is available in the literature to show the effect of coating LNO on CAM performance. This paper aims to quantify the effect of LNO coating on the electrochemical performance of a nickel-rich CAM. The electrochemical performance parameters that are studied are the capacity, cycling performance, and rate performance of the coated-CAM; and the effectiveness of the coating to prevent the side reactions at the ASE and CAM interface is out of the scope of this study. To eliminate the effect of side reactions at the ASE and CAM interface, we conduct all tests in the organic liquid electrolyte (OLE) cells to solely present the effect of coating on the CAM performance. For this purpose, 0.5 wt.% and 1 wt.% LNO are used to coat the LiNi_0.6Mn_0.2Co_0.2O₂ (NMC-60) CAM through two synthesizing methods. Consequently, the effects of the synthesizing method and the coating weight percentage on the NMC-60 performance are presented. Full article

All-solid-state batteries (ASSBs) are a promising response to the need for safety and high energy density of large-scale energy storage systems in challenging applications such as electric vehicles and grid integration. ASSBs based on sulfide solid electrolytes (SEs) have attracted much attention because of their high ionic conductivity and wide electrochemical windows of the sulfide SEs. Here, we study the electrochemical performance of ASSBs using composite electrodes prepared via two processes (simple mixture and solution processes) and varying the ionic conductor additive (80Li₂S∙20P₂S₅ and argyrodite-type Li₆PS₅Cl). The composite electrodes consist of lithium-silicate-coated LiNi_1/3Mn_1/3Co_1/3O₂ (NMC), a sulfide SE, and carbon additives. The charge-transfer resistance at the interface of the solid electrolyte and NMC is the main parameter related to the ASSB’s status. This value decreases when the composite electrodes are prepared via a solution process. The lithium silicate coating and the use of a high-Li-ion additive conductor are also important to reduce the interfacial resistance and achieve high initial capacities (140 mAh g⁻¹). Full article

Li_6.3La₃Zr_1.65W_0.35O₁₂ (LLZO)-Li₆PS₅Cl (LPSC) composite electrolytes and all-solid-state cells containing LLZO-LPSC were fabricated by cold pressing at room temperature. The LPSC:LLZO ratio was varied, and the microstructure, ionic conductivity, and electrochemical performance of the corresponding composite electrolytes were investigated; the ionic conductivity of the composite electrolytes was three or four orders of magnitude higher than that of LLZO. The high conductivity of the composite electrolytes was attributed to the enhanced relative density and the rule of mixture for soft LPSC particles with high lithium-ion conductivity (~10⁻⁴ S·cm⁻¹). The specific capacities of all-solid-state cells (ASSCs) consisting of a LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode and the composite electrolytes of LLZO:LPSC = 7:3 and 6:4 were 163 and 167 mAh·g⁻¹, respectively, at 0.1 C and room temperature. Moreover, the charge–discharge curves of the ASSCs with the composite electrolytes revealed that a good interfacial contact was successfully formed between the NCM811 cathode and the LLZO-LPSC composite electrolyte. Full article