Uncontrollable Li dendrite growth and infinite volume fluctuation during durative plating and stripping process gravely hinder the application of metallic Li electrode in lithium-oxygen batteries.Herein,oxygen vacancy...Uncontrollable Li dendrite growth and infinite volume fluctuation during durative plating and stripping process gravely hinder the application of metallic Li electrode in lithium-oxygen batteries.Herein,oxygen vacancy-rich TiO_(2)(Vo-TiO_(2))nanoparticles(NPs)uniformly dispersing on Ti_(3)C_(2)T_(x)(Vo-TiO_(2)/Ti_(3)C_(2) T_(x))with excellent lithiophilicity feature are presented as effective composite anodes,on which a dense and uniform Li growth behavior is observed.Based on electrochemical studies,mutiphysics simulation and theoretical calculation,it is found that Vo-TiO_(2) coupling with three dimensional(3 D)conductive Ti_(3)C_(2) T_(x) MXene forms highly ordered lithiophilic sites which succeed in guiding Li ions flux and adsorption,thus modulating the uniform Li nucleation and growth.As a result,this composite electrode is capable of preserving Li with high areal capacity of~10 mAh cm^(-2) without the presence of dendrites and large volume expansion.Consequently,the as-prepared Vo-TiO_(2)/Ti_(3)C_(2) T_(x)@Li anode shows outstanding performance including low voltage hysteresis(~19 mV)and superior durability(over 750 h).When assembling with the Vo-TiO_(2)/Ti_(3)C_(2) T_(x)@Li anodes,lithium-oxygen batteries also deliver enhanced cycling stability and improved rate performance.This work demonstrates the effectiveness of oxygen vacancies in guiding Li nucleating and plating behavior at initial stage and brings a promising strategy for promoting the development of advanced Li metal-based batteries.展开更多
设计和制备具有优异稳定性和高活性的催化剂对于提高锂-氧气电池的性能至关重要.由于其可调节的结构及促进氧还原反应和析氧反应动力学的有效性,异质结构催化剂引起了广泛的研究兴趣.在这项工作中,CuCo_(2)S_(4)/CoS_(1.097)多元金属硫...设计和制备具有优异稳定性和高活性的催化剂对于提高锂-氧气电池的性能至关重要.由于其可调节的结构及促进氧还原反应和析氧反应动力学的有效性,异质结构催化剂引起了广泛的研究兴趣.在这项工作中,CuCo_(2)S_(4)/CoS_(1.097)多元金属硫化物被证明是锂-氧气电池氧电极反应的有效电催化剂.密度泛函理论计算表明,CuCo_(2)S_(4)/CoS_(1.097)的电子结构在异相界面处受到调控,有利于优化氧电极反应过程中间体的吸附,最终加速氧电极反应动力学.实验结果表明,基于CuCo_(2)S_(4)/CoS_(1.097)的锂-氧气电池在100 m A g^(-1)下具有26,727.8 m A h g^(-1)的高比容量和超过267次循环的出色耐久性.该工作为锂-氧气电池高性能正极材料的设计和构造提供了新视角.展开更多
基金financially supported by the National Natural Science Foundation of China(Grant No.21905033)the Science and Technology Department of Sichuan Province(Grant No.2019YJ0503)the State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(2020P4FZG02A)。
文摘Uncontrollable Li dendrite growth and infinite volume fluctuation during durative plating and stripping process gravely hinder the application of metallic Li electrode in lithium-oxygen batteries.Herein,oxygen vacancy-rich TiO_(2)(Vo-TiO_(2))nanoparticles(NPs)uniformly dispersing on Ti_(3)C_(2)T_(x)(Vo-TiO_(2)/Ti_(3)C_(2) T_(x))with excellent lithiophilicity feature are presented as effective composite anodes,on which a dense and uniform Li growth behavior is observed.Based on electrochemical studies,mutiphysics simulation and theoretical calculation,it is found that Vo-TiO_(2) coupling with three dimensional(3 D)conductive Ti_(3)C_(2) T_(x) MXene forms highly ordered lithiophilic sites which succeed in guiding Li ions flux and adsorption,thus modulating the uniform Li nucleation and growth.As a result,this composite electrode is capable of preserving Li with high areal capacity of~10 mAh cm^(-2) without the presence of dendrites and large volume expansion.Consequently,the as-prepared Vo-TiO_(2)/Ti_(3)C_(2) T_(x)@Li anode shows outstanding performance including low voltage hysteresis(~19 mV)and superior durability(over 750 h).When assembling with the Vo-TiO_(2)/Ti_(3)C_(2) T_(x)@Li anodes,lithium-oxygen batteries also deliver enhanced cycling stability and improved rate performance.This work demonstrates the effectiveness of oxygen vacancies in guiding Li nucleating and plating behavior at initial stage and brings a promising strategy for promoting the development of advanced Li metal-based batteries.
基金supported by the National Natural Science Foundation of China(21905033 and 52271201)the Science and Technology Department of Sichuan Province(2022YFG0100)the State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(2020P4FZG02A)。
文摘设计和制备具有优异稳定性和高活性的催化剂对于提高锂-氧气电池的性能至关重要.由于其可调节的结构及促进氧还原反应和析氧反应动力学的有效性,异质结构催化剂引起了广泛的研究兴趣.在这项工作中,CuCo_(2)S_(4)/CoS_(1.097)多元金属硫化物被证明是锂-氧气电池氧电极反应的有效电催化剂.密度泛函理论计算表明,CuCo_(2)S_(4)/CoS_(1.097)的电子结构在异相界面处受到调控,有利于优化氧电极反应过程中间体的吸附,最终加速氧电极反应动力学.实验结果表明,基于CuCo_(2)S_(4)/CoS_(1.097)的锂-氧气电池在100 m A g^(-1)下具有26,727.8 m A h g^(-1)的高比容量和超过267次循环的出色耐久性.该工作为锂-氧气电池高性能正极材料的设计和构造提供了新视角.
基金supported by the National Natural Science Foundation of China(21905033)the Science and Technology Department of Sichuan Province(2019YJ0503)the State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization(2020P4FZG02A)。
文摘构造阳离子空位被认为是一种可以提高电催化剂活性的有效策略.然而,在材料表面高效地引入阳离子空位仍面临诸多挑战.另外,关于阳离子空位对锂-氧气(Li-O_(2))电池氧电极反应活性的影响少有报道.本文报道了在V_(2)C MXene表面原位构造富含钒空位的五氧化二钒(V_(2-x)O_(5)@V_(2)C MXene)的方法,并系统研究了该材料对Li-O_(2)电池氧电极反应的双功能催化活性.结果表明,基于V_(2-x)O_(5)@V_(2)C MXene的Li-O_(2)电池具有良好的性能.其在100 mA g^(-1)电流密度下展示出高的能量效率(83.4%)和优异的循环性能(超过500次循环).密度泛函理论计算结果表明,阳离子钒空位的存在可以提供大量活性位点以降低Li-O_(2)电池氧电极反应能垒并促进反应物的吸附.本工作表明,通过构造阳离子金属空位来调节材料表面电子结构是提高过渡金属氧化物电催化活性的有效路径.
