Atomic-Scale Cryo-TEM Studies of the Electrochemistry of Redox Mediator in Li-O2 Batteries.

Rechargeable aprotic lithium (Li)-oxygen battery (LOB) is a potential next-generation energy storage technology because of its high theoretical specific energy. However, the role of redox mediator on the oxide electrochemistry remains unclear. This is partly due to the intrinsic complexity of the battery chemistry and the lack of in-depth studies of oxygen electrodes at the atomic level by reliable techniques. Herein, cryo-transmission electron microscopy (cryo-TEM) is used to study how the redox mediator LiI affects the oxygen electrochemistry in LOBs. It is revealed that with or without LiI in the electrolyte, the discharge products are plate-like LiOH or toroidal Li2 O2 , respectively. The I2 assists the decomposition of LiOH via the formation of LiIO3 in the charge process. In addition, a LiI protective layer is formed on the Li anode surface by the shuttle of I3 - , which inhibits the parasitic Li/electrolyte reaction and improves the cycle performance of the LOBs. The LOBs returned to 2e- oxygen reduction reaction (ORR) to produce Li2 O2 after the LiI in the electrolyte is consumed. This work provides new insight on the role of redox mediator on the complex electrochemistry in LOBs which may aid the design LOBs for practical applications.

Size-Dependent Chemomechanical Failure of Sulfide Solid Electrolyte Particles during Electrochemical Reaction with Lithium.

The very high ionic conductivity of Li10GeP2S12 (LGPS) solid electrolyte (SE) makes it a promising candidate SE for solid-state batteries in electrical vehicles. However, chemomechanical failure, whose mechanism remains unclear, has plagued its widespread applications. Here, we report in situ imaging lithiation-induced failure of LGPS SE. We revealed a strong size effect in the chemomechanical failure of LGPS particles: namely, when the particle size is greater than 3 µm, fracture/pulverization occurred; when the particle size is between 1 and 3 µm, microcracks emerged; when the particle size is less than 1 µm, no chemomechanical failure was observed. This strong size effect is interpreted by the interplay between elastic energy storage and dissipation. Our finding has important implications for the design of high-performance LGPS SE, for example, by reducing the particle size to less than 1 µm the chemomechanical failure of LGPS SE can be mitigated.

Promoting favorable interfacial properties in lithium-based batteries using chlorine-rich sulfide inorganic solid-state electrolytes.

The use of inorganic solid-state electrolytes is considered a viable strategy for developing high-energy Li-based metal batteries. However, suppression of parasitic interfacial reactions and growth of unfavorable Li metal depositions upon cycling are challenging aspects and not yet fully addressed. Here, to better understand these phenomena, we investigate various sulfide inorganic solid electrolytes (SEs), i.e., Li7-xPS6-xClx (x = 0.6, 1.0, 1.3, 1.45, and 1.6), via ex situ and in situ physicochemical and electrochemical measurements. We found that the Cl distribution and the cooling process applied during the SE synthesis strongly influence the evolution of the Li|SE interface in terms of microstructure, interphase composition, and morphology. Indeed, for a SE with a moderate chlorine content (i.e., x = 1.3) and obtained via a slow cooling process after sintering, the Cl atoms are located on the surface of the SE grains as interconnected LiCl nanoparticles that form an extended LiCl-based framework. This peculiar microstructure facilitates the migration of the Cl ions to the Li|SE interface during electrochemical cycling, thus, favouring the formation of a LiCl-rich interphase layer capable of improving the battery cycling performances.

Room Temperature Halide-Eutectic Solid Electrolytes with Viscous Feature and Ultrahigh Ionic Conductivity.

A viscous feature is beneficial for a solid electrolyte with respect to assembling solid-state batteries, which can change the solid-solid contacts from point to face. Here, novel halide-based deep eutectic solid electrolytes (DESEs) prepared by a facile ball milling method is reported. The mixture of halides triggers the deep eutectic phenomena by intermolecular interactions, leading to diverse morphologies and viscous statuses in terms of composition. Chemical- and micro-structure analyses via the cryogenic technique reveal that the LiCl and LiF nanoparticles are dispersed in an amorphous halide matrix, which endow freely mobile ions for fast ion transport. The optimized DESE thus achieves low activation energy and high ionic conductivity of 16 mS cm-1 at room temperature, one of the highest values among various electrolytes so far. By integrating with the active materials to form a composite cathode, the viscous DESE yields a super-dense composite pellet which possesses intensively enhanced ionic conductivity in contrast to those formed by the sulfide-based electrolyte additives, demonstrating an attractive application prospect.

Enabling Long Cycle Life and High Rate Iron Difluoride Based Lithium Batteries by In Situ Cathode Surface Modification.

Metals fluorides (MFs) are potential conversion cathodes to replace commercial intercalation cathodes. However, the application of MFs is impeded by their poor electronic/ionic conductivity and severe decomposition of electrolyte. Here, a composite cathode of FeF2 and polymer-derived carbon (FeF2 @PDC) with excellent cycling performance is reported. The composite cathode is composed of nanorod-shaped FeF2 embedded in PDC matrix with excellent mechanical strength and electronic/ionic conductivity. The FeF2 @PDC enables a reversible capacity of 500 mAh g-1 with a record long cycle lifetime of 1900 cycles. Remarkably, the FeF2 @PDC can be cycled at a record rate of 60 C with a reversible capacity of 107 mAh g-1 after 500 cycles. Advanced electron microscopy reveals that the in situ formation of stable Fe3 O4 layers on the surface of FeF2 prevents the electrolyte decomposition and leaching of iron (Fe), thus enhancing the cyclability. The results provide a new understanding to FeF2 electrochemistry, and a strategy to radically improve the electrochemical performance of FeF2 cathode for lithium-ion battery applications.

In situ observation of cracking and self-healing of solid electrolyte interphases during lithium deposition.

The growth of lithium (Li) whiskers is detrimental to Li batteries. However, it remains a challenge to directly track Li whisker growth. Here we report in situ observations of electrochemically induced Li deposition under a CO2 atmosphere inside an environmental transmission electron microscope. We find that the morphology of individual Li deposits is strongly influenced by the competing processes of cracking and self-healing of the solid electrolyte interphase (SEI). When cracking overwhelms self-healing, the directional growth of Li whiskers predominates. In contrast, when self-healing dominates over cracking, the isotropic growth of round Li particles prevails. The Li deposition rate and SEI constituent can be tuned to control the Li morphologies. We reveal a new "weak-spot" mode of Li dendrite growth, which is attributed to the operation of the Bardeen-Herring growth mechanism in the whisker's cross section. This work has implications for the control of Li dendrite growth in Li batteries.

Ultrastable Anode/Electrolyte Interface in Solid-State Lithium-Metal Batteries Using LiCux Nanowire Network Host.

High interfacial resistance and uncontrollable lithium (Li) dendrite are major challenges in solid-state Li-metal batteries (SSLMBs), as they lead to premature short-circuiting and failure of SSLMBs. Here, we report the synthesis of a composite anode comprising a three-dimensional LiCux nanowire network host infiltrated with Li (Li* anode) with low interfacial impedance and superior electrochemical performance. The Li* anode is fabricated by dissolving Cu foil into molten Li followed by solidification. The Li* anode exhibits good wettability with Li6.4La3Zr1.4Ta0.6O12 (LLZTO) and high mechanical strength, rendering low Li*/LLZTO interfacial impedance, homogeneous deposition of Li, and suppression of Li dendrites. Consequently, the Li* anode-based symmetric cells and full cells with LiNi0.88Co0.1Al0.02O2 (NCA), LiFePO4 (LFP), and FeF2 cathodes deliver remarkable electrochemical performance. Specifically, the Li*/LLZTO/Li* symmetrical cell achieves a remarkably long cycle lifetime of 10 000 h with 0.1 mA·cm-2; the Li*/LLZTO/NCA full cell maintains capacity retention of 73.4% after 500 cycles at 0.5C; and all-solid-state Li*/LLZTO/FeF2 full cell achieves a reversible capacity of 147 mAh·g-1 after 500 cycles at 100 mA·g-1. This work demonstrates potential design tactics for an ultrastable Li*/garnet interface to enable high-performance SSLMBs.

Unraveling the Reaction Mechanism of FeS2 as a Li-Ion Battery Cathode.

Iron pyrite (FeS2) is a promising lithium-ion battery cathode material because of its low cost and ultrahigh energy density (1671 Wh kg-1). However, its reaction mechanisms are still controversial. In this work, we find that different from the conventional belief that an intermediate phase Li2FeS2 is formed followed by Fe/Li2S composites at the initial discharge, it undergoes a one-step reaction (FeS2 → Fe + Li2S) or a two-step reaction (FeS2 → FeS + Li2S → Fe + Li2S), which depends on the current rate and temperature. In the charge process, it undergoes a two-step reaction: phase transition Fe + Li2S → FeS at about 1.74 V and generation of elemental sulfur (Li2S → S, 2.30 V). FeS is a mackinawite phase that is formed on the interface of Li2S via heteroepitaxial growth. Subsequent cycles involves a combination reaction of FeS and S. The reaction mechanism suggests that FeS2 suffers from the demerits of both FeS and S, such as a large volume change, voltage hysteresis, and polysulfide dissolution. These findings would help us to understand the intrinsic capacity fading of FeS2 and provide guidelines to improve its electrochemical performances.

In situ imaging electrocatalytic CO2 reduction and evolution reactions in all-solid-state Li-CO2 nanobatteries.

Li-CO2 batteries are promising energy storage devices owing to their high energy density and possible applications for CO2 capture. However, still some critical issues, such as high charging overpotential and poor cycling stability caused by the sluggish decomposition of Li2CO3 discharge products, need to be addressed before the practical applications of Li-CO2 batteries. Exploring highly efficient catalysts and understanding their catalytic mechanisms for the CO2 reduction reaction (CORR) and evolution reaction (COER) are critical for the application of Li-CO2 batteries. However, the direct imaging of electrocatalysis during CORR and COER is still elusive. Herein, we report the in situ imaging of electrocatalysis during CORR and COER in a Li-CO2 nanobattery using a Ni-Ru-coated α-MnO2 nanowire (Ni-Ru/MnO2) cathode in an advanced aberration corrected environmental transmission electron microscope. During the CORR, a thick Li2CO3 and carbon mixture layer was formed on the surface of the Ni-Ru/MnO2 nanowires via 4Li+ + 3CO2 + 4e-→ 2Li2CO3 + C. During the COER, the as-formed Li2CO3 decomposed via 2Li2CO3→ 2CO2 + O2 + 4Li+ + 4e-, while the as-formed amorphous carbon remained. In contrast, the decomposition of Li2CO3 on bare MnO2 nanowires was difficult, underscoring the important Ni-Ru bimetal electrocatalytic role in facilitating the COER. Our results provide an important understanding of the CO2 chemistry in Li-CO2 batteries, possibly helping in the designing of Li-CO2 batteries for energy storage applications.

Foster replantation of fingertip using neighbouring digital artery in a young child.

UNLABELLED: Reconstruction of an amputated fingertip in a young child demands special techniques for success. We report a 2.5-year-old female patient with an amputated left index fingertip with the vascular defect being too severe to perform the usual replantation. Comparing several methods, we used the neighbouring digital artery as the feeding artery to perform foster replantation. Finally, the patient was satisfied with the appearance and function of her fingers. The clinical case, techniques, results are described and discussed. We consider it a useful technique, especially for those with a rather severe vascular defect. PATIENT: A 2.5-year-old girl suffered a crush amputation of the left index fingertip. Only the flexor tendon of the amputated fingertip was connected to the proximal finger tissue and the blood supply was completely lost (Figure 1). METHODS: The distal amputated fingertip was fixed using Kirschner wire under general anaesthesia. Then, microsurgery operation was carried out immediately to replant this amputated fingertip. Both ulnar and radial digital arteries were avulsed, while the dorsal vein was intact and the digital nerve was also surviving. The integrity of blood vessels was too traumatised to connect to the proximal part. In the case of the distal part of the ulnar artery of the injured index finger, the blood supply was established by anastomosing the distal end of the amputated tip and the radial artery of the middle finger, which was the feeding artery (Figure 2). A 11/0 nylon suture was used. The dorsal vein and digital nerve were repaired by means of microsurgical anastomosis. The wound was covered with the dorsal skin of the middle finger and the palmar skin of the index finger to form a skin pedicle, and then, immobility of the two fingers was maintained to prevent avulsion. RESULT: The index tip obtained good blood supply and survived completely (Figure 3). Detachment of the index and middle finger was performed after 3 weeks, and both of the fingers showed good blood supply (Figure 4). The appearance and function of the index and middle fingers were satisfactory 3 months postoperatively.