Recent advances in metal-organic frameworks for lithium metal anode protection

The lithium metal battery has been considered as a promising candidate for next generation batteries.However,safety concerns caused by uncontrollable lithium dendrite growth on lithium anode are severely hampering the commercial application.Metal-organic frameworks(MOFs)become one of the most attractive materials due to the high porosity,structural designability and tunability.With unique open channels and pores as well as functional components in MOFs,the transportation and deposition of lithium ions can be regulated,which leads to enhanced electrochemical prope rties.Various strategies for lithium metal protection are proposed in recent wo rks on applications of MOFs in lithium metal batteries.In this review,we highlight latest key approaches in this field and discuss the prospects for MOFs in advanced Li anodes.     

TiC/C core/shell nanowires arrays as advanced anode of sodium ion batteries

High-perfo rmance anodes of sodium ion batteries(SIBs)largely depends on rational architecture design and binder-free smart hybridization.Herein,we report TiC/C core/shell nanowires arrays prepared by a one-step chemical vapor deposition(CVD)method and apply it as the anode of SIBs for the first time.The conductive TiC core is intimately decorated with carbon shell.The as-obtained TiC/C nanowires are homogeneously grown on the substrate and show core/shell heterostructure and porous architecture with high electronic conductivity and reinforced stability.Owing to these merits,the TiC/C electrode displays good rate performance and outstanding cycling performance with a capacity of 135.3 mAh/g at 0.1 A/g and superior capacity retention of 90.14%after 1000 cycles at 2 A/g.The reported strategy would provide a promising way to construct binder-free arrays electrodes for sodium ion storage.     

废旧锂离子电池正极材料资源化回收与再生

随着电子设备的普及和电动汽车行业的迅速崛起,作为提供能量来源的锂离子电池发挥着重要的作用。以钴酸锂、磷酸铁锂以及三元正极材料为代表的锂离子电池产销量不断增加;与此同时,为了提供更长的续航时间以及续航稳定性,新型锂离子电池材料的研究工作也在不断推进。在此背景下,锂离子电池正极材料的失效、废弃以及资源化回收再生的过程就显得愈发重要,如何在下游解决报废锂离子电池处理的问题也逐渐提上日程。基于此,本文分别从湿法和火法再生两个角度对废旧锂离子电池正极材料的回收和再生过程进行了介绍,包括回收条件优化的方法、较为新颖的回收再生方法以及再生材料的性能等,并总结了回收再生过程的杂质元素,包括铝、铜等元素对再生材料结构和性能的影响以及工业上常用的回收废旧锂离子电池的方法和环境影响。最后对锂离子电池回收的方法进行总结并进行展望。     

中空核壳结构Ni1.2Co0.8P@N-C钠离子电池负极材料的制备及拉曼研究

本文设计制备了一种新型的氮掺杂碳包覆镍钴双金属磷化物中空核壳结构纳米立方体(Ni_1.2Co_0.8P@N-C)作为钠离子电池负极材料. 该材料以镍钴类普鲁士蓝(PBA)纳米粒子为模板,先后经水热法、磷化法和高温碳化处理后合成. 将其作为活性材料应用在钠离子电池中,该材料展现出优异的循环稳定性,当以100 mA·g^-1的电流密度循环至200圈时,该材料的库仑效率保持在99.3%. 进一步通过对不同电位下Ni_1.2Co_0.8P@N-C材料中的氮掺杂碳进行原位拉曼光谱测试,结果显示钠离子在氮掺杂的碳壳中的脱嵌行为具有较大程度的可逆性,研究结果对钠离子电池充放电过程的后续电化学研究提供了有价值的信息.     

锂硫电池硫正极催化转换反应的研究进展

单质硫作为电池的正极材料,其电化学过程历经多个步骤,完全放电生成最终产物是一个2电子反应. 低阶多硫化锂的生成需克服一定的能垒,且由Li₂S₂得到一个电子还原生成Li₂S的反应是速控步骤. 硫正极的反应动力学是决定锂硫电池电化学性能,如比能量、比功率、低温性能等的关键因素. 提高速控步骤的反应动力学还能加速可溶性多硫化锂Li₂S₄向不溶性Li₂S₂和Li₂S的转化,有利于减缓或消除多硫化锂的“穿梭效应”. 近年,已有大量的过渡金属氧化物、硫化物、碳化物、氮化物、磷化物,单原子催化剂和氧化还原电子中继体等被应用于催化硫正极反应,提高了电极的电化学性能和循环稳定性. 但是,目前详细的催化反应机制尚不完全清晰. 本文重点综述了这些化合物在硫正极反应中的作用机制,总结了近年来的研究进展,并对硫正极催化转换反应的研究和发展进行了展望.     

Antiperovskite Intermetallic Nanoparticles for Enhanced Oxygen Reduction

Antiperovskite Co₃InC_0.7N_0.3 nanomaterials with highly enhanced oxygen reduction reaction (ORR) performance were prepared by tuning nitrogen contents through a metal–organic framework (MOF)‐derived strategy. The nanomaterial surpasses all reported noble‐metal‐free antiperovskites and even most perovskites in terms of onset potential (0.957 V at J=0.1 mA cm^?2) and half‐wave potential (0.854 V). The OER and zinc–air battery performance demonstrate its multifunctional oxygen catalytic activities. DFT calculation was performed and for the first time, a 4 e^? dissociative ORR pathway on (200) facets of antiperovskite was revealed. Free energy studies showed that nitrogen substitution could strengthen the OH desorption as well as hydrogenation that accounts for the enhanced ORR performance. This work expands the scope for material design via tailoring the nitrogen contents for optimal reaction free energy and hence performance of the antiperovskite system.     

Deciphering an Abnormal Layered‐Tunnel Heterostructure Induced by Chemical Substitution for the Sodium Oxide Cathode

Demands for large‐scale energy storage systems have driven the development of layered transition‐metal oxide cathodes for room‐temperature rechargeable sodium ion batteries (SIBs). Now, an abnormal layered‐tunnel heterostructure Na_0.44Co_0.1Mn_0.9O₂ cathode material induced by chemical element substitution is reported. By virtue of beneficial synergistic effects, this layered‐tunnel electrode shows outstanding electrochemical performance in sodium half‐cell system and excellent compatibility with hard carbon anode in sodium full‐cell system. The underlying formation process, charge compensation mechanism, phase transition, and sodium‐ion storage electrochemistry are clearly articulated and confirmed through combined analyses of in situ high‐energy X‐ray diffraction and ex situ X‐ray absorption spectroscopy as well as operando X‐ray diffraction. This crystal structure engineering regulation strategy offers a future outlook into advanced cathode materials for SIBs.     

A Low‐Cost and Environmentally Friendly Mixed Polyanionic Cathode for Sodium‐Ion Storage

Sodium‐ion batteries (NIBs) are the most promising alternatives to lithium‐ion batteries in the development of renewable energy sources. The advancement of NIBs depends on the exploration of new electrode materials and fundamental understanding of working mechanisms. Herein, via experimental and simulation methods, we develop a mixed polyanionic compound, Na₂Fe(C₂O₄)SO₄?H₂O, as a cathode for NIBs. Thanks to its rigid three dimensional framework and the combined inductive effects from oxalate and sulfate, it delivered reversible Na insertion/desertion at average discharging voltages of 3.5 and 3.1 V for 500 cycles with Coulombic efficiencies of ca. 99 %. In situ synchrotron X‐ray measurements and DFT calculations demonstrate the Fe²⁺/Fe³⁺ redox reactions contribute to electron compensation during Na⁺ desertion/insertion. The study suggests mixed polyanionic frameworks may provide promising materials for Na ion storage with the merits of low cost and environmental friendliness.     

Dendrite‐Free Sodium Metal Anodes Enabled by a Sodium Benzenedithiolate‐Rich Protection Layer

Sodium metal is an ideal anode material for metal rechargeable batteries, owing to its high theoretical capacity (1166 mAh g^?1), low cost, and earth‐abundance. However, the dendritic growth upon Na plating, stemming from unstable solid electrolyte interphase (SEI) film, is a major and most notable problem. Here, a sodium benzenedithiolate (PhS₂Na₂)‐rich protection layer is synthesized in situ on sodium by a facile method that effectively prevents dendrite growth in the carbonate electrolyte, leading to stabilized sodium metal electrodeposition for 400 cycles (800 h) of repeated plating/stripping at a current density of 1 mA cm^?2. The organic salt, PhS₂Na₂, is found to be a critical component in the protection layer. This finding opens up a new and promising avenue, based on organic sodium slats, to stabilize sodium metals with a protection layer.     

In Situ Electropolymerization Enables Ultrafast Long Cycle Life and High‐Voltage Organic Cathodes for Lithium Batteries

Organic cathode materials have attracted extensive attention because of their diverse structures, facile synthesis, and environmental friendliness. However, they often suffer from insufficient cycling stability caused by the dissolution problem, poor rate performance, and low voltages. An in situ electropolymerization method was developed to stabilize and enhance organic cathodes for lithium batteries. 4,4′,4′′‐Tris(carbazol‐9‐yl)‐triphenylamine (TCTA) was employed because carbazole groups can be polymerized under an electric field and they may serve as high‐voltage redox‐active centers. The electropolymerized TCTA electrodes demonstrated excellent electrochemical performance with a high discharge voltage of 3.95 V, ultrafast rate capability of 20 A g^?1, and a long cycle life of 5000 cycles. Our findings provide a new strategy to address the dissolution issue and they explore the molecular design of organic electrode materials for use in rechargeable batteries.