Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305.
Stanford Nano Shared Facilities, Stanford University, Stanford, CA 94305.
Proc Natl Acad Sci U S A. 2017 Nov 14;114(46):12138-12143. doi: 10.1073/pnas.1708224114. Epub 2017 Oct 30.
Lithium, with its high theoretical specific capacity and lowest electrochemical potential, has been recognized as the ultimate negative electrode material for next-generation lithium-based high-energy-density batteries. However, a key challenge that has yet to be overcome is the inferior reversibility of Li plating and stripping, typically thought to be related to the uncontrollable morphology evolution of the Li anode during cycling. Here we show that Li-metal texturing (preferential crystallographic orientation) occurs during electrochemical deposition, which governs the morphological change of the Li anode. X-ray diffraction pole-figure analysis demonstrates that the texture of Li deposits is primarily dependent on the type of additive or cross-over molecule from the cathode side. With adsorbed additives, like LiNO and polysulfide, the lithium deposits are strongly textured, with Li (110) planes parallel to the substrate, and thus exhibit uniform, rounded morphology. A growth diagram of lithium deposits is given to connect various texture and morphology scenarios for different battery electrolytes. This understanding of lithium electrocrystallization from the crystallographic point of view provides significant insight for future lithium anode materials design in high-energy-density batteries.
锂因其具有高的理论比容量和最低的电化学电势,已被认为是下一代基于锂的高能量密度电池的终极负极材料。然而,一个尚未克服的关键挑战是锂电镀和剥离的可逆性较差,通常认为这与锂阳极在循环过程中不可控的形态演变有关。在这里,我们表明,在电化学沉积过程中会发生锂金属织构化(优先晶面取向),这控制着锂阳极的形态变化。X 射线衍射极图分析表明,锂沉积物的织构主要取决于来自阴极侧的添加剂或交叉分子的类型。对于吸附添加剂,如 LiNO 和多硫化物,锂沉积物具有强烈的织构,Li(110)面与基底平行,因此表现出均匀、圆形的形态。给出了一个锂沉积物的生长图,以连接不同电池电解质的各种织构和形态情况。从晶体学角度对锂电结晶的这种理解为高能密度电池中未来的锂阳极材料设计提供了重要的启示。