RESUMO
Herein, we report halide nanocomposite solid electrolytes (HNSEs) that integrate diverse oxides with alterations that allow tuning of their ionic conductivity, (electro)chemical stability, and specific density. A two-step mechanochemical process enabled the synthesis of multimetal (or nonmetal) HNSEs, MO2-2Li2ZrCl6, as verified by pair distribution function and X-ray diffraction analyses. The multimetal (or nonmetal) HNSE strategy increases the ionic conductivity of Li2ZrCl6 from 0.40 to 0.82 mS cm-1. Additionally, cyclic voltammetry test findings corroborated the enhanced passivating properties of the HNSEs. Notably, incorporating SiO2 into HNSEs leads to a substantial reduction in the specific density of HNSEs, demonstrating their strong potential for achieving a high energy density and lowering costs. Fluorinated SiO2-2Li2ZrCl5F HNSEs exhibited enhanced interfacial compatibility with Li6PS5Cl and LiCoO2 electrodes. Cells employing SiO2-2Li2ZrCl5F with LiCoO2 exhibit superior electrochemical performance delivering the initial discharge capacity of 162 mA h g-1 with 93.7% capacity retention at the 100th cycle at 60 °C.
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A solid-solution cathode of LiCoPO4-LiNiPO4 was investigated as a potential candidate for use with the Li4Ti5O12 (LTO) anode in Li-ion batteries. A pre-synthesized nickel-cobalt hydroxide precursor is mixed with lithium and phosphate sources by wet ball milling, which results in the final product, LiNiyCo1-yPO4 (LNCP) by subsequent heat treatment. Crystal structure and morphology of the product were analyzed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). Its XRD patterns show that LNCP is primarily a single-phase compound and has olivine-type XRD patterns similar to its parent compounds, LiCoPO4 and LiNiPO4. Synchrotron X-ray absorption spectroscopy (XAS) analysis, however, indicates that Ni doping in LiCoPO4 is unfavorable because Ni2+ is not actively involved in the electrochemical reaction. Consequently, it reduces the charge storage capability of the LNCP cathode. Additionally, ex situ XRD analysis of cycled electrodes confirms the formation of the electrochemically inactive rock salt-type NiO phase. The discharge capacity of the LNCP cathode is entirely associated with the Co3+/Co2+ redox couple. The electrochemical evaluation demonstrated that the LNCP cathode paired with the LTO anode produced a 3.12 V battery with an energy density of 184 Wh kg-1 based on the cathode mass.
RESUMO
Designing highly conductive and (electro)chemical stable inorganic solid electrolytes using cost-effective materials is crucial for developing all-solid-state batteries. Here, we report halide nanocomposite solid electrolytes (HNSEs) ZrO2(-ACl)-A2ZrCl6 (A = Li or Na) that demonstrate improved ionic conductivities at 30 °C, from 0.40 to 1.3 mS cm-1 and from 0.011 to 0.11 mS cm-1 for Li+ and Na+, respectively, compared to A2ZrCl6, and improved compatibility with sulfide solid electrolytes. The mechanochemical method employing Li2O for the HNSEs synthesis enables the formation of nanostructured networks that promote interfacial superionic conduction. Via density functional theory calculations combined with synchrotron X-ray and 6Li nuclear magnetic resonance measurements and analyses, we demonstrate that interfacial oxygen-substituted compounds are responsible for the boosted interfacial conduction mechanism. Compared to state-of-the-art Li2ZrCl6, the fluorinated ZrO2-2Li2ZrCl5F HNSE shows improved high-voltage stability and interfacial compatibility with Li6PS5Cl and layered lithium transition metal oxide-based positive electrodes without detrimentally affecting Li+ conductivity. We also report the assembly and testing of a Li-In||LiNi0.88Co0.11Mn0.01O2 all-solid-state lab-scale cell operating at 30 °C and 70 MPa and capable of delivering a specific discharge of 115 mAh g-1 after almost 2000 cycles at 400 mA g-1.
RESUMO
Grid-scale energy storage applications can benefit from rechargeable sodium-ion batteries. As a potential material for making non-cobalt, nickel-free, cost-effective cathodes, earth-abundant Na2/3Fe1/2Mn1/2O2 is of particular interest. However, Mn3+ ions are particularly susceptible to the Jahn-Teller effect, which can lead to an unstable structure and continuous capacity degradation. Modifying the crystal structure by aliovalent doping is considered an effective strategy to alleviate the Jahn-Teller effect. Using a sol-gel synthesis route followed by heat treatment, we succeeded in preparing an Mg-doped Na2/3Fe1-yMnyO2 cathode. Its electrochemical properties and charge compensation mechanism were then studied using synchrotron-based X-ray absorption spectroscopy and in situ X-ray diffraction techniques. The results revealed that Mg doping reduced the number of Mn3+ Jahn-Teller centers and alleviated high voltage phase transition. However, Mg doping was unable to suppress the P2-P'2 phase transition at a low voltage discharge. An initial discharge capacity of about 196 mAh g-1 was obtained at a current density of 20 mAh g-1, and 60% of rate capability was maintained at a current density of 200 mAh g-1 in a voltage range of 1.5-4.3 V. This study will greatly contribute to the ongoing search for advanced and efficient cathodes from earth-abundant elements for rechargeable sodium-ion batteries operable at room temperature.
RESUMO
Activation of oxygen redox during the first cycle has been reported as the main trigger of voltage hysteresis during further cycles in high-energy-density Li-rich 3d-transition-metal layered oxides. However, it remains unclear whether hysteresis only occurs due to oxygen redox. Here, it is identified that the voltage hysteresis can highly correlate to cationic reduction during discharge in the Li-rich layered oxide, Li1.2 Ni0.4 Mn0.4 O2 . In this material, the potential region of discharge accompanied by hysteresis is apparently separated from that of discharge unrelated to hysteresis. The quantitative analysis of soft/hard X-ray absorption spectroscopies discloses that hysteresis is associated with an incomplete cationic reduction of Ni during discharge. The galvanostatic intermittent titration technique shows that the inevitable energy consumption caused by hysteresis corresponds to an overpotential of 0.3 V. The results unveil that hysteresis can also be affected by cationic redox in Li-rich layered cathodes, implying that oxygen redox cannot be the only reason for the evolution of voltage hysteresis. Therefore, appropriate control of both cationic and anionic redox of Li-rich layered oxides will allow them to reach their maximum energy density and efficiency.
RESUMO
We explore a phase engineering strategy to improve the electrochemical performance of transition metal sulfides (TMSs) in anode materials for lithium-ion batteries (LIBs). A one-pot hydrothermal approach has been employed to synthesize MoS2 nanostructures. MoS2 and MoO3 phases can be readily controlled by straightforward calcination in the (200-300) °C temperature range. An optimized temperature of 250 °C yields a phase-engineered MoO3@MoS2 hybrid, while 200 and 300 °C produce single MoS2 and MoO3 phases. When tested in LIBs anode, the optimized MoO3@MoS2 hybrid outperforms the pristine MoS2 and MoO3 counterparts. With above 99% Coulombic efficiency (CE), the hybrid anode retains its capacity of 564 mAh g-1 after 100 cycles, and maintains a capacity of 278 mAh g-1 at 700 mA g-1 current density. These favorable characteristics are attributed to the formation of MoO3 passivation surface layer on MoS2 and reactive interfaces between the two phases, which facilitate the Li-ion insertion/extraction, successively improving MoO3@MoS2 anode performance.
RESUMO
Sodium-ion batteries (SIBs) hold great potential for use in large-scale grid storage applications owing to their low energy cost compared to lithium analogs. The symmetrical SIBs employing Na3 V2 (PO4 )3 (NVP) as both the cathode and anode are considered very promising due to negligible volume changes and longer cycle life. However, the structural changes associated with the electrochemical reactions of symmetrical SIBs employing NVP have not been widely studied. Previous studies on symmetrical SIBs employing NVP are believed to undergo one mole of Na+ storage during the electrochemical reaction. However, in this study, it is shown that there are significant differences during the electrochemical reaction of the symmetrical NVP system. The symmetrical sodium-ion cell undergoes ≈2 moles of Na+ reaction (intercalation and deintercalation) instead of 1 mole of Na+ . A simultaneous formation of Na5 V2 (PO4 )3 phase in the anode and NaV2 (PO4 )3 phase in the cathode is revealed by synchrotron-based X-ray diffraction and X-ray absorption spectroscopy. A symmetrical NVP cell can deliver a stable capacity of ≈99 mAh g-1 , (based on the mass of the cathode) by simultaneously utilizing V3+ /V2+ redox in anode and V3+ /V4+ redox in cathode. The current study provides new insights for the development of high-energy symmetrical NIBs for future use.
RESUMO
Owing to their high Li+ conductivities, mechanical sinterability, and solution processability, sulfide Li argyrodites have attracted much attention as enablers in the development of high-performance all-solid-state batteries with practicability. However, solution-processable Li argyrodites have been developed only for a composition of Li6PS5X (X = Cl, Br, I) with insufficiently high Li+ conductivities (â¼10-4 S cm-1). Herein, we report the highest Li+ conductivity of 0.54 mS cm-1 at 30 °C (Li6.5P0.5Ge0.5S5I) for solution-processable iodine-based Li argyrodites. A comparative investigation of three iodine-based argyrodites of unsubstituted and Ge- and Sn-substituted solution-processed Li6PS5I with varied heat-treatment temperature elucidates the effect of microstructural evolution on Li+ conductivity. Notably, local nanostructures consisting of argyrodite nanocrystallites in solution-processed Li6.5P0.5Ge0.5S5I have been directly captured by cryogenic transmission electron microscopy, which is a first for sulfide solid electrolyte materials. Specifically, the promising electrochemical performances of all-solid-state batteries at 30 °C employing LiCoO2 electrodes tailored by the infiltration of Li6.5P0.5Ge0.5S5I-ethanol solutions are successfully demonstrated.