Enabling structural and interfacial stability of 5 V spinel LiNi0.5Mn1.5O4 cathode by a coherent interface

Spinel LiNi_(0.5)Mn_(1.5)O_(4)(LNMO),a 5 V class high voltage cathode,has been regarded as an attractive candidate to further improve the energy density of lithium-ion battery.The issue simultaneously enabling side stability and maintaining high interfacial kinetics,however,has not yet been resolved.Herein,we design a coherent Li_(1.3)A_(l0.3)Ti_(1.7)(PO)_(4)(LATP)layer that is crystally connected to the spinel LNMO host lattices,which offers fast lithium ions transportation as well as enhances the mechanical stability that prevents the particle fracture.Furthermore,the inactive Li_(3)BO_(3)(LBO)coating layer inhibits the corrosion of transition metals and continuous side reactions.Consequently,the coherent-engineered LNMO-LATPLBO cathode material exhibits superior electrochemical cycling stability in a window of 3.0–5.0 V,for example a high-capacity retention that is 89.7%after 500 cycles at 200 m A g-1obtained and enhanced rate performance(85.1 m A h g^(-1)at 800 m A g^(-1))when tested with a LiPF6-based carbonate electrolyte.Our work presents a new approach of engineering 5 V class spinel oxide cathode that combines interfacial coherent crystal lattice design and surface coating.

Interfacial nitrogen engineering of robust silicon/MXene anode toward high energy solid-state lithium-ion batteries

Replacing the conventional carbonate electrolyte by solid-state electrolyte (SSE) will offer improved safety for lithium-ion batteries.To further improve the energy density,Silicon (Si) is attractive for next generation solid-state battery (SSB) because of its high specific capacity and low cost.High energy density and safe Si-based SSB,however,is plagued by large volume change that leads to poor mechanical stability and slow lithium ions transportation at the multiple interfaces between Si and SSE.Herein,we designed a self-integrated and monolithic Si/two dimensional layered T_(3)C_(2)T_(x)(MXene,T_(x) stands for terminal functional groups) electrode architecture with interfacial nitrogen engineering.During a heat treatment process,the polyacrylonitrile not only converts into amorphous carbon (a-C) that shells Si but also forms robust interfacial nitrogen chemical bonds that anchors Si and MXene.During repeated lithiation and delithiation processes,the robust interfacial engineered Si/MXene configuration enhances the mechanical adhesion between Si and MXene that improves the structure stability but also contributes to form stable solid-electrolyte interphase (SEI).In addition,the N-MXene provides fast lithium ions transportation pathways.Consequently,the Si/MXene with interfacial nitrogen engineering (denoted as Si-N-MXene) deliveres high-rate performance with a specific capacity of 1498 m Ah g^(-1) at a high current of 6.4 A g^(-1).A Si-N-MXene/NMC full cell exhibited a capacity retention of 80.5%after 200 cycles.The Si-N-MXene electrode is also applied to SSB and shows a relative stable cycling over 100 cycles,demonstrating the versatility of this concept.

Cu nanowire array with designed interphases enabling high performance Si anode toward flexible lithium-ion battery

To meet the growing demand for wearable smart electronic devices,the development of flexible lithium-ion batteries(LIBs)is essential.Silicon is an ideal candidate for the anode material of flexible lithium-ion batteries due to its high specific capacity,low working potential,and earth abundance.The largest challenge in developing a flexible silicon anode is how to maintain structural integrity and ensure stable electrochemical reactions during external deformation.In this work,we propose a novel design for fabricating core–shell electrodes based on a copper nanowire(CuNW)array core and magnetron sputtered Si/C shell.The nanowire array structure has characteristics of bending under longitudinal stress and twisting under transverse stress,which helps to maintain the mechanical stability of the structure during electrode bending and cycling.The low-temperature annealing generates a small amount of Cu3Si alloy,which enhances the connection strength between Si and the conductive network and solves the poor conductivity problem of Si,which is known as a semiconductor material.This unique configuration design of CuNW@Si@C-400℃ leads to stable long cycle performance of 1109 mAh∙g^(-1) after 1000 cycles and excellent rate performance of 500 mAh∙g^(-1) at a current density of 10 A∙g^(-1).Furthermore,the CuNW@Si@C-400℃||LiFePO_(4)(LFP)full battery demonstrates excellent flexibility,with a capacity retention of more than 96%after 100 bends.This study provides a promising strategy for the development of flexible lithium-ion batteries.

Tuning the electron transport behavior at Li/LATP interface for enhanced cyclability of solid-state Li batteries

An interlayer is usually employed to tackle the interfacial instability issue between solid electrolytes(SEs)and Li metal caused by the side reaction.However,the failure mechanism of the ionic conductor interlayers,especially the influence from electron penetration,remains largely unknown.Herein,using Li1.3Al0.3Ti1.7(PO4)3(LATP)as the model SE and LiF as the interlayer,we use metal semiconductor contact barrier theory to reveal the failure origin of Li/LiF@LATP interface based on the calculation results of density functional theory(DFT),in which electrons can easily tunnel through the LiF grain boundary with F vacancies due to its narrow barrier width against electron injection,followed by the reduction of LATP.Remarkably,an Al-LiF bilayer between Li/LATP is found to dramatically promote the interfacial stability,due to the highly increased barrier width and homogenized electric field at the interface.Consequently,the Li symmetric cells with Al-LiF bilayer can exhibit excellent cyclability of more than 2,000 h superior to that interlayered by LiF monolayer(~860 h).Moreover,the Li/Al-LiF@LATP/LiFePO4 solid-state batteries deliver a capacity retention of 83.2%after 350 cycles at 0.5 C.Our findings emphasize the importance of tuning the electron transport behavior by optimizing the potential barrier for the interface design in high-performance solid-state batteries.

Liquid-phase sintering enabling mixed ionic-electronic interphases and free-standing composite cathode architecture toward high energy solid-state battery

Solid-state batteries(SSBs)will potentially offer increased energy density and,more importantly,improved safety for next generation lithium-ion(Li-ion)batteries.One enabling technology is solid-state composite cathodes with high operating voltage and area capacity.Current composite cathode manufacturing technologies,however,suffer from large interfacial resistance and low active mass loading that with excessive amounts of polymer electrolytes and conductive additives.Here,we report a liquidphase sintering technology that offers mixed ionic-electronic interphases and free-standing electrode architecture design,which eventually contribute to high area capacity.A small amount(~4 wt.%)of lithium hydroxide(LiOH)and boric acid(H_(3)BO_(3))with low melting point are utilized as sintering additives that infiltrate into single-crystal Ni-rich LiNi_(0.8)Mn_(0.1)Co_(0.1)(NMC811)particles at a moderately elevated temperature(~350℃)in a liquid state,which not only enable intimate physical contact but also promote the densification process.In addition,the liquid-phase additives react and transform to ionic-conductive lithium boron oxide,together with the indium tin oxide(ITO)nanoparticle coating,mixed ionic-electronic interphases of composite cathode are successfully fabricated.Furthermore,the liquid-phase sintering performed at high-temperature(~800℃)also enables the fabrication of highly dense and thick composite cathodes with a novel free-standing architecture.The promising performance characteristics of such composite cathodes,for example,delivering an area capacity above 8 mAh·cm^(−2) within a wide voltage window up to 4.4 V,open new opportunities for SSBs with a high energy density of 500 Wh·kg^(−1) for safer portable electronic and electrical transport.