Mg2SiO4/Si-Coated Disproportionated SiO Composite Anodes with High Initial Coulombic Efficiency for Lithium Ion Batteries.

Silicon monoxide (SiO) is considered as one of the most promising anode material candidates for next-generation high-energy-density lithium ion batteries (LIBs) due to its high specific capacity and relatively lower volume expansion than that of Si. However, a large number of irreversible products are formed during the first charging and discharging process, resulting in a low initial Coulombic efficiency (ICE) of SiO. Herein, we report an economical and convenient method to increase the ICE of SiO without sacrificing its specific capacity by a solid reaction between magnesium silicide (Mg2Si) and micron-sized SiO. The reaction product (named MSO) exhibits a unique core-shell structure with uniformly distributed Mg2SiO4 and Si as the shell and disproportionated SiO as the core. MSO exhibits a superior ICE and a high reversible capacity of 81.7% and 1306.1 mAh g-1, respectively, which can be further increased to 88.7% and 1446.4 mAh g-1 after carbon coating, and improved cyclic stability compared to bare SiO. This work provides a simple yet effective strategy to address the low ICE issue of SiO anode materials to promote the practical application of SiO.

Reactivating Li2 O with Nano-Sn to Achieve Ultrahigh Initial Coulombic Efficiency SiO Anodes for Li-Ion Batteries.

The application of SiO anodes in Li-ion batteries is greatly restricted by its low initial coulombic efficiency (ICE). Usually, a pre-lithiation procedure is necessary to improve the ICE, but the available technologies are associated with safety issues. Metal (M)-mixed SiO shows great promise to address these issues by reactivating Li2 O through the reaction M+Li2 O→MOx +Li+ , which is the inverse reaction to that occurring at MOx anodes. Sn is found to be a good choice of metal for this concept. Nanoscale Sn-mixed SiO composites are prepared by mechanical milling. Sn forms an outstanding conductive phase, which boosts the reaction kinetics and also reactivates the Li2 O byproduct. Sn/SiO (1:2 w/w) delivers a significant improvement in ICE from 66.5 % to 85.5 %. A higher ICE value of >90 % is obtained when the Sn content is ≥50 wt %. However, additional electrolyte decomposition occurs, which is catalyzed by Sn. In addition, coarsening of the nano-Sn material reduces the inverse conversion reactivity of Sn/Li2 O and subsequently results in rapid capacity fading. The quantitative analysis indicates that, in contrast to transition metals, the alloying and dealloying nature of Sn gives a 50 % improvement in reversible capacity, attributed to Sn/Li2 O. This work gives a general strategy to choose metals for increasing the ICE of SiOx and metal oxides.

Confining Al-Li alloys between pre-constructed conductive buffers for advanced aluminum anodes.

An aluminum anode with pre-constructed two-layer conductive buffers was prepared to restrict the expanding Al-Li alloy inside, and provide continuous electron pathways for promising electrical contact. The full cell demonstrates superior cycling stability (0.0352% capacity decay per cycle for 400 cycles at 0.2C) and outstanding rate capability.

New perspective to understand the effect of electrochemical prelithiation behaviors on silicon monoxide.

Electrochemical prelithiation is a facile, effective and extensively used method to improve the initial coulombic efficiency of SiO. However, much less research attention has been devoted to prelithiation effect on initial several cycles. Here, we introduce a new perspective to evaluate the prelithiation behaviors, which could understand in depth the electrochemical prelithiation behaviors and their effects on the following two cycles. Then X-ray photoelectron spectroscopy was further performed to pinpoint the reaction products. It has been found that the quantity of irreversible Li4SiO4, Li2O and SEI (Li2CO3 and LiF) and reversible Li x Si are increasing as the prelithiation time extending. When the prelithiation time extending over 20 min, only alloy reaction of Si has been revealed. The regeneration of SEI discloses at least 7% capacity loss in the first cycle which depends on the prelithiated time. However, the reformation of SEI in the second cycles reveals 3% capacity loss. Because the coulombic efficiencies are independent on prelithiated time in the second cycle which indicates only one discharge/charge cycle is enough to form integrated SEI and adequate irreversible Li4SiO4 and Li2O except part of unreactive SiO x .