在透射电子显微镜中直接观察材料锂化动力学行为

锂离子电池的电极材料是决定其性能的关键因素之一,电极材料的储锂与失效机制是开发高性能锂离子电池的重要基础科学问题。本文在透射电子显微镜内以目标材料为工作电极搭建锂离子半电池,利用透射电子显微镜的原子结构表征技术对电极材料在锂化动态反应过程中的形貌、成分、结构等进行原位表征,开展锂离子动力学过程和电化学储能机制研究。结果表明,硅负极纳米线的锂化以及能源利用率存在明显的尺寸效应,在二维材料MoS2中首次观察到了锂离子嵌入导致的2H-1T的相转变过程。本研究对理解锂离子电池工作的原子机制和开发新型锂离子电池材料具有重要意义。

Recovery of valuable metals from lepidolite by atmosphere leaching and kinetics on dissolution of lithium

The lepidolite located in Yichun, Jiangxi Province, China, was adopted to investigate the recovery of alkali metals and leaching kinetics of lithium with sulphuric acid solution under atmospheric pressure. The results show that the recoveries of alkali metals were achieved under the leaching conditions: mass ratio of lepidolite with particle size less than 180 μm to sulphuric acid 1.2, leaching temperature 411 K, liquid-solid ratio 2.5∶1, and leaching time 10 h. Under the selected conditions for leaching experiment, the leaching rates of lithium, potassium, rubidium and caesium are 94.18%, 93.70%, 91.81% and 89.22%, respectively. The X-ray diffraction analysis for leaching residue indicates that no insoluble product forms during leaching. The chemical compositions of leaching residue reveal that trace iron, manganese and calcium disappear after acid leaching. The kinetics of leaching process for lithium follows shrinking core model of mixed control and the apparent activation energy is 17.21 kJ/mol. The reaction orders with respect to sulphuric acid concentration and liquid-solid ratio are determined to be 2.85 and 1.66, respectively. A semi-empirical rate equation was obtained to describe the leaching process. The kinetic analysis shows that the leaching process is controlled by diffusion through the insoluble layer of the associated minerals.

Kinetics of leaching lithium from α-spodumene in enhanced acid treatment using HF/H_2SO_4 as medium

An enhanced leaching of Li fromα-spodumene was carried out using a mixture of hydrofluoric and sulfuric acid(HF/H2SO4)as the medium.Based on the optimized leaching conditions,the leaching kinetics of Li was investigated in an ore/HF/H2SO4 ratio of 1:3:2 g:mL:mL with leaching temperature ranging from 50 to 100°C.The results indicate that the leaching kinetics of Li fitted well with a model based on the shrinking core model.In addition,the leaching rate of Li was controlled by chemical reactions and diffusion through the product layers.The apparent activation energy Ea was calculated to be 32.68 kJ/mol.Solid films were formed because of the generation of insoluble products such as cryolithionite(Na3Li2Al2F12),cryolite(Na3AlF6),calcium fluoride(CaF2),potassium cryolite(K2AlF5),aluminum fluoride(AlF3),and fluorosilicates(Na2SiF6 or KNaSiF6).Furthermore,the effects of the ore/HF ratio and leaching temperature on the leaching behavior of Li,Al and Si were investigated.The results indicate that the ore/HF ratio and leaching temperature could clearly affect the distribution of HF molecules on the leaching of Li,Al and Si,which are important for the selective leaching of Li over Al and Si with this fluorine-based chemical method.

Modification of natural graphite using pitch through dynamical melt-carbonization

The graphite was modified using pitch through dynamical melt-carbonization, and the effects of modification temperature and the amount of pitch on the characteristics of graphite were investigated. The structure and characteristics of the graphite were determined by X-ray diffractometry(XRD), scanning electron microscopy(SEM), particle size analysis and electrochemical measurements. The results show that the modified graphite has a disordered carbon/graphite composite structure, larger average particle diameter, greater tap density, and better electrochemical characteristics than the untreated graphite. The sample coated with 10% pitch dynamical melt-carbonized at 400 ℃ for 3 h and heat-treated at 850 ℃ for 2 h has better electrochemical performances with a reversible capacity of 360.5 mA·h/g, a irreversible capacity of 41.0 mA·h/g, and an initial coulombic efficiency of 89.8% compared with natural graphite and disordered carbon. The cycling stability of the Li/C cell with modified graphite as anodes is improved, and its capacity retention ratio at the 30th cycle is up to 94.37%.

Boosting reaction kinetics and reversibility in Mott-Schottky VS/MoS heterojunctions for enhanced lithium storage

Heterostructures have lately been recognized as a viable implement to achieve high-energy Li-ion batteries(LIBs) because the as-formed built-in electric field can greatly accelerate the charge transfer kinetics. Herein, we have constructed the Mott-Schottky heterostructured VS2/MoS2 hybrids with tailorable 1T/2H phase based on their matchable formation energy, which are made of metallic and few-layered VS2 vertically grown on MoS2 surface. The density functional theory(DFT) calculations unveil that such heterojunctions drive the rearrangement of energy band with a facilitated reaction kinetics and enhance the Li adsorption energy more than twice compared to the MoS2 surface. Furthermore, the VS2 catalytically expedites the Li–S bond fracture and meantime the enriched Mo6+ enables the sulfur anchoring toward the oriented reaction with Li+to form Li2S, synergistically enhancing the reversibility of electrochemical redox. Consequently, the as-obtained VS2/MoS2 hybrids deliver a very large specific capacity of 1273 m Ah g^-1 at 0.1 A g^-1 with 61% retention even at 5 A g^-1. It can also stabilize 100 cycles at 0.5 A g^-1 and 500 cycles at 1 A g^-1. The findings provide in-depth insights into engineering heterojunctions towards the enhancement of reaction kinetics and reversibility for LIBs.