Quantitatively analyzing the failure processes of rechargeable Li metal batteries.

Practical use of lithium (Li) metal for high–energy density lithium metal batteries has been prevented by the continuous formation of Li dendrites, electrochemically isolated Li metal, and the irreversible formation of solid electrolyte interphases (SEIs). Differentiating and quantifying these inactive Li species are key to understand the failure mode. Here, using operando nuclear magnetic resonance (NMR) spectroscopy together with ex situ titration gas chromatography (TGC) and mass spectrometry titration (MST) techniques, we established a solid foundation for quantifying the evolution of dead Li metal and SEI separately. The existence of LiH is identified, which causes deviation in the quantification results of dead Li metal obtained by these three techniques. The formation of inactive Li under various operating conditions has been studied quantitatively, which revealed a general “two-stage” failure process for the Li metal. The combined techniques presented here establish a benchmark to unravel the complex failure mechanism of Li metal

P2-Na0.67 Alx Mn1-x O2 : Cost-Effective, Stable and High-Rate Sodium Electrodes by Suppressing Phase Transitions and Enhancing Sodium Cation Mobility.

Sodium layered P2-stacking Na0.67 MnO2 materials have shown great promise for sodium-ion batteries. However, the undesired Jahn-Teller effect of the Mn4+ /Mn3+ redox couple and multiple biphasic structural transitions during charge/discharge of the materials lead to anisotropic structure expansion and rapid capacity decay. Herein, by introducing abundant Al into the transition-metal layers to decrease the number of Mn3+ , we obtain the low cost pure P2-type Na0.67 Alx Mn1-x O2 (x=0.05, 0.1 and 0.2) materials with high structural stability and promising performance. The Al-doping effect on the long/short range structural evolutions and electrochemical performances is further investigated by combining in situ synchrotron XRD and solid-state NMR techniques. Our results reveal that Al-doping alleviates the phase transformations thus giving rise to better cycling life, and leads to a larger spacing of Na+ layer thus producing a remarkable rate capability of 96 mAh g-1 at 1200 mA g-1

Unraveling (electro)-chemical stability and interfacial reactions of Li 10 SnP 2 S 12 in all-solid-state Li batteries

Abstract(#br)Li 10 SnP 2 S 12 (LSPS) with high ionic conductivity and moderate price is a promising solid electrolyte for all-solid-state batteries. However, the instability of LSPS and LSPS/electrodes interfaces would cause poor cycle performance issues in the LSPS-based all-solid-state batteries, which have not been well understood. Herein, we address and unravel the decomposition products of LSPS and their Li + transfer characteristics, especially on the surface of LSPS/electrodes by using solid-state nuclear magnetic resonance (ss NMR) spectroscopy coupled with X-ray photoelectron spectroscopy (XPS). The results reveal that the high mechanical energy during ball-milling process leads to the decomposition of LSPS into Li 4 SnS 4 and Li 3 PS 4 . During charge/discharge cycling, specific capacity fading of batteries originates from the formation of new interfacial layer at LSPS/Acetylene black cathode and LSPS/Li metal anode interfaces. Furthermore, our results demonstrate that the rough and porous morphology of the interface formed after cycling, rather than the decomposition products, is the critical factor which results in the increases of the interfacial resistance at LSPS/Li interface and serious formation of Li dendrite. Our results highlight the significant roles of (electro)chemical and interfacial stability of sulfide solid electrolyte in the development of all-solid-state batteries

Highly-stable P2-Na 0.67 MnO 2 electrode enabled by lattice tailoring and surface engineering

Abstract(#br)One of the key challenges of sodium ion batteries is to develop sustainable, low-cost and high capacity cathodes, and this is the reason that layered sodium manganese oxides have attracted so much attention. However, the undesired phase transitions and poor electrolyte-electrode interfacial stability facilitate their capacity decay and limit their practical applications. Herein, we design a novel Al 2 O 3 @Na 0.67 Zn 0.1 Mn 0.9 O 2 electrode to mitigate these problems, by taking the advantages of both structural stabilization and surface passivation via Zn 2+ substitution and Al 2 O 3 atomic layered deposition (ALD), respectively. Long-range and local structural analyses during charging/discharging processes indicate that P2-P2’ phase transformation can be suppressed by substituting proper amount of Mn 3+ Jahn-Teller centers with Zn 2+ , whereas excessive Zn 2+ leads to P2-OP4 structure transition at low sodium contents and facilitates the electrode degradations. Furthermore, the homogeneous and robust cathode electrolyte interphase (CEI) layers formed on the Al 2 O 3 -coated electrodes effectively hinder the organic electrolytes from further decomposition. Therefore, our synergetic strategy of Zn 2+ substitution and ALD surface engineering remarkably boosts the cycling performance of P2-Na 0.67 MnO 2 and provides some new insights into the designing of highly stable cathode electrodes for sustainable sodium ion batteries

Solid‐State NMR and MRI Spectroscopy for Li/Na Batteries: Materials, Interface, and In Situ Characterization

Enhancing the electrochemical performance of batteries, including the lifespan, energy, and power densities, is an everlasting quest for the rechargeable battery community. However, the dynamic and coupled (electro)chemical processes that occur in the electrode materials as well as at the electrode/electrolyte interfaces complicate the investigation of their working and decay mechanisms. Herein, the recent developments and applications of solid-state nuclear magnetic resonance (ssNMR) and magnetic resonance imaging (MRI) techniques in Li/Na batteries are reviewed. Several typical cases including the applications of NMR spectroscopy for the investigation of the pristine structure and the dynamic structural evolution of materials are first emphasized. The NMR applications in analyzing the solid electrolyte interfaces (SEI) on the electrode are further concluded, involving the identification of SEI components and investigation of ionic motion through the interfaces. Beyond, the new development of in situ NMR and MRI techniques are highlighted, including their advantages, challenges, applications and the design principle of in situ cell. In the end, a prospect about how to use ssNMR in battery research from the perspectives of materials, interface, and in situ NMR, aiming at obtaining deeper insight of batteries with the assistance of ssNMR is represented

A Nearly Zero-Strain Li-Rich Rock-Salt Oxide with Multielectron Redox Reactions as a Cathode for Li-Ion Batteries

Li-rich oxide cathodes are drawing increasing attention as next-generation cathode materials for the development of high-energy-density Li-ion batteries due to their strikingly high capacities. However, transition-metal migration, irreversible structural phase transformations, and the irreversible release of oxygen are responsible for rapid capacity and voltage decay. This study reports a Li-rich cation-ordered rock-salt oxide LixV0.4Ti0.4O2(LVTO, x = 0.97/1.2) with space group Fd3¯ m that delivers a high capacity of over 250 mAh g-1and capacity retention up to 89% after 50 cycles. A comprehensive experimental analysis confirms that the capacity can be attributed to the reversible V3+/V5+multielectron cationic redox reactions and a minor contribution from reversible anionic redox reactions. Importantly, LVTO exhibits nearly zero-strain behavior upon (dis)charge cycling cycles, which is associated with reversible V migration from octahedral to tetrahedral sites. Our results demonstrate that Li-rich rock-salt oxide LVTO could be a promising cobalt-free cathode material for Li-ion batteries

The stability of P2-layered sodium transition metal oxides in ambient atmospheres

Air-stability is a critical challenge faced by layered sodium transition metal oxide cathodes. Here, the authors depict a general and in-depth model of the structural/chemical evolution of P2-type layered oxides in air and propose an evaluation rule for the air-stability of layered sodium cathodes