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The sulfide solid electrolyte Li4SnS4 has garnered considerable interest due to its exceptional moisture durability, which is attributed to its stable hydrated state. However, a major limitation of certain sulfide solid electrolytes, including Li4SnS4, is their low reduction durability, which limits their application in the negative electrodes of all-solid-state batteries and impedes qualitative material development assessments. In this study, we introduced a quantitative and straightforward method for evaluating the reductive decomposition of Li4SnS4 to better understand its degradation mechanism. The configuration of the electrochemical evaluation cell was modified from SUS|Li4SnS4|Li to SUS|Li4SnS4|Li3PS4|Li, allowing for stabilization of the reference potential of the counter electrode. The reductive decomposition potential of Li4SnS4 was quantitatively assessed by using cyclic voltammetry in a two-layer electrochemical evaluation cell. We observed a minor irreversible reduction current below +1.2 V and a pronounced decomposition peak at +1.0 V. Notably, reductive decomposition continued below 0 V, which is typically the onset point for Li electrodeposition. Postreduction, the solid electrolyte was comprehensively analyzed through optical microscopy, X-ray diffraction, and X-ray absorption spectroscopy. These analyzes revealed the following: (i) The SnS44- unit in Li4SnS4 initially decomposes into Li2S and ß-Sn with the dissociation of the Sn-S bond; (ii) the resulting ß-Sn forms LixSn alloys such as Li0.4Sn; and (iii) the ongoing reductive decomposition reaction is facilitated by the electronic conductivity of these LixSn alloys. These findings offer crucial methodological and mechanistic insights into the development of higher-performance solid electrolyte materials.
RESUMO
We successfully prepared an Fe- and Li-containing polysulfide positive electrode material (Li8FeS5-Li2FeS2 composite) that shows a high specific capacity (>500 mA h g-1) with improved rate capability in all-solid-state cells. High-resolution TEM analysis indicated the coexistence of small crystallites of high-conductivity Li2FeS2 and FeS, as well as low-crystallinity Li2S, in the composite, and this microstructure is responsible for the improved battery performance.
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The application of lithium metal as a negative electrode in all-solid-state batteries shows promise for optimizing battery safety and energy density. However, further development relies on a detailed understanding of the chemo-mechanical issues at the interface between the lithium metal and solid electrolyte (SE). In this study, crack formation inside the sulfide SE (Li3PS4: LPS) layers during battery operation was visualized using in situ X-ray computed tomography (X-ray CT). Moreover, the degradation mechanism that causes short-circuiting was proposed based on a combination of the X-ray CT results and scanning electron microscopy images after short-circuiting. The primary cause of short-circuiting was a chemical reaction in which LPS was reduced at the lithium interface. The LPS expanded during decomposition, thereby forming small cracks. Lithium penetrated the small cracks to form new interfaces with fresh LPS on the interior of the LPS layers. This combination of reduction-expansion-cracking of LPS was repeated at these new interfaces. Lithium clusters eventually formed, thereby generating large cracks due to stress concentration. Lithium penetrated these large cracks easily, finally causing short-circuiting. Therefore, preventing the reduction reaction at the interface between the SE and lithium metal is effective in suppressing degradation. In fact, LPS-LiI electrolytes, which are highly stable to reduction, were demonstrated to prevent the repeated degradation mechanism. These findings will promote all-solid-state lithium-metal battery development by providing valuable insight into the design of the interface between SEs and lithium, where the selection of a suitable SE is vital.
RESUMO
Sulfide solid electrolytes with high ionic conductivity and high air stability must be developed for manufacturing sulfide all-solid-state batteries. Li10GeP2S12-type and argyrodite-type solid electrolytes exhibit a high ionic conductivity of â¼10-2 S cm-1 at room temperature, while emitting toxic H2S gas when exposed to air. We focused on hexagonal Li4SnS4 prepared by mechanochemical treatment because it comprises air-stable SnS4 tetrahedra and shows higher ionic conductivity than orthorhombic Li4SnS4 prepared by solid-phase synthesis. Herein, to enhance the ionic conductivity of hexagonal Li4SnS4, LiI was added to Li4SnS4 by mechanochemical treatment. The ionic conductivity of 0.43LiI·0.57Li4SnS4 increased by 3.6 times compared with that of Li4SnS4. XRD patterns of Li4SnS4 with LiI showed peak-shifting to lower angles, indicating that introduction of I-, which has a large ionic radius, expanded the Li conduction paths. Furthermore, Li3PS4, which is the most air-stable in the Li2S-P2S5 system and has higher ionic conductivity than Li4SnS4, was added to the LiI-Li4SnS4 system. We found that 0.37LiI·0.25Li3PS4·0.38Li4SnS4 sintered at 200 °C showed the highest ionic conductivity of 5.5 × 10-4 S cm-1 at 30 °C in the hexagonal Li4SnS4-based solid electrolytes. The rate performance of an all-solid-state battery using 0.37LiI·0.25Li3PS4·0.38Li4SnS4 heated at 200 °C was higher than those obtained using Li4SnS4 and 0.43LiI·0.57Li4SnS4. In addition, it exhibited similar air stability to Li4SnS4 by formation of LiI·3H2O in air. Therefore, addition of LiI and Li3PS4 to hexagonal Li4SnS4 by mechanochemical treatment is an effective way to enhance ionic conductivity without decreasing the air stability of Li4SnS4.
RESUMO
The reaction uniformity of LiCoO2 composite positive electrodes in all-solid-state cells was compared quantitatively by investigating the Raman band shifts corresponding to the state-of-charge (SOC) of LiCoO2. The quantitative SOC analysis was conducted using the Raman imaging data of composite electrodes with smaller or larger solid electrolytes. The electrodes exhibited different reaction uniformity although the cells showed similar initial charge capacities and average SOC. In the case of larger solid electrolytes, most LiCoO2 particles showed higher or lower SOC than the average SOC, and lower battery performance. The quantitative analysis of SOC in each LiCoO2 electrode demonstrated that a variable SOC outside the average SOC resulted in larger irreversible capacity and lower rate performance. The quantitative SOC analysis newly developed in the present study is a useful technique for designing composite electrodes showing higher battery performance.
RESUMO
Long-lasting all-solid-state batteries can be achieved by preventing side reactions in the composite electrodes comprising electrode active materials and solid electrolytes. Typically, the battery performance can be enhanced through the use of robust solid electrolytes that are resistant to oxidation and decomposition. In this study, the thermal stability of sulfide solid electrolytes Li3PS4 and Li4SnS4 toward oxide positive electrode active materials was estimated by investigating the occurrence of side reactions at the electrolyte-electrode interfaces when the composite electrodes are heated in an accelerated aging test: Li4SnS4 showed higher thermal stability because of the suppression of the substitution reaction between S and O. Moreover, thermally stable sulfide solid electrolytes are amenable to an improved cell construction process. The sintering (pelletizing and subsequent heating) of the composite electrodes with Li4SnS4 as the solid electrolyte allowed the manufacture of dense electrodes that exhibited increased ionic conductivity, thereby enhancing the battery performance.
RESUMO
The dynamic changes of ionic conduction path in the cross-sectional graphite composite electrodes of bulk-type all-solid-state lithium batteries have been monitored using operando confocal microscopic observations for color changes of graphite in response to their stage structures. The ionic conduction path decreased in the cross-sectional direction as cycle numbers increased, with simultaneous capacity degradation. The local reactivity of lithiation and delithiation was evaluated by image analysis considering state-of-charge (SOC) values. Electrode thickness changes were examined from the confocal microscope images obtained in the operando observations. The results revealed that voids and cracks were formed during cycle tests and that the thickness gradually increased. These cracks and voids were one of the main contributors to the limitation of ionic conduction paths in the depth direction. Operando microscopic observation and subsequent image analysis elucidated not only the morphological changes of active materials but also the differences in local SOC changes in the electrode.
RESUMO
A new crystalline lithium-ion conducting material, Li4SnS4 with an ortho-composition, was prepared by a mechanochemical technique and subsequent heat treatment. Synchrotron X-ray powder diffraction was used to analyze the crystal structure, revealing a space group of P63/ mmc and cell parameters of a = 4.01254(4) Å and c = 6.39076(8) Å. Analysis of a heat-treated hexagonal Li4SnS4 sample revealed that both lithium and tin occupied either of two adjacent tetrahedral sites, resulting in fractional occupation of the tetrahedral site (Li, 0.375; Sn, 0.125). The heat-treated hexagonal Li4SnS4 had an ionic conductivity of 1.1 × 10-4 S cm-1 at room temperature and a conduction activation energy of 32 kJ mol-1. Moreover, the heat-treated Li4SnS4 exhibited a higher chemical stability in air than the Li3PS4 glass-ceramic.
RESUMO
Sulfide-based all-solid-state lithium batteries are a next-generation power source composed of the inorganic solid electrolytes which are incombustible and have high ionic conductivity. Positive electrode composites comprising LiNi1/3Mn1/3Co1/3O2 (NMC) and 75Li2S·25P2S5 (LPS) glass electrolytes exhibit excellent charge-discharge cycle performance and are promising candidates for realizing all-solid-state batteries. The thermal stabilities of NMC-LPS composites have been investigated by transmission electron microscopy (TEM), which indicated that an exothermal reaction could be attributed to the crystallization of the LPS glass. To further understand the origin of the exothermic reaction, in this study, the precipitated crystalline phase of LPS glass in the NMC-LPS composite was examined. In situ TEM observations revealed that the ß-Li3PS4 precipitated at approximately 200 °C, and then Li4P2S6 and Li2S precipitated at approximately 400 °C. Because the Li4P2S6 and Li2S crystalline phases do not precipitate in the single LPS glass, the interfacial contact between LPS and NMC has a significant influence on both the LPS crystallization behavior and the exothermal reaction in the NMC-LPS composites.