Liu Pengcheng, Wang Yixian, Hao Hongchang, Basu Swastik, Feng Xuyong, Xu Yixin, Boscoboinik Jorge Anibal, Nanda Jagjit, Watt John, Mitlin David
Materials Science and Engineering Program & Texas Materials Institute (TMI), The University of Texas at Austin, Austin, TX, 78712-1591, USA.
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, 11973, USA.
Adv Mater. 2020 Dec;32(49):e2002908. doi: 10.1002/adma.202002908. Epub 2020 Nov 2.
This is the first report of successful potassium metal battery anode cycling with an aluminum-based rather than copper-based current collector. Dendrite-free plating/stripping is achieved through improved electrolyte wetting, employing an aluminum-powder-coated aluminum foil "Al@Al," without any modification of the support surface chemistry or electrolyte additives. The reservoir-free Al@Al half-cell is stable at 1000 cycles (1950 h) at 0.5 mA cm , with 98.9% cycling Coulombic efficiency and 0.085 V overpotential. The pre-potassiated cell is stable through a wide current range, including 130 cycles (2600 min) at 3.0 mA cm , with 0.178 V overpotential. Al@Al is fully wetted by a 4 m potassium bis(fluorosulfonyl)imide-dimethoxyethane electrolyte (θ = 0°), producing a uniform solid electrolyte interphase (SEI) during the initial galvanostatic formation cycles. On planar aluminum foil with a nearly identical surface oxide, the electrolyte wets poorly (θ = 52°). This correlates with coarse irregular SEI clumps at formation, 3D potassium islands with further SEI coarsening during plating/stripping, possibly dead potassium metal on stripped surfaces, and rapid failure. The electrochemical stability of Al@Al versus planar Al is not related to differences in potassiophilicity (nearly identical) as obtained from thermal wetting experiments. Planar Cu foils are also poorly electrolyte-wetted and become dendritic. The key fundamental takeaway is that the incomplete electrolyte wetting of collectors results in early onset of SEI instability and dendrites.
这是首次关于使用铝基而非铜基集流体实现钾金属电池阳极循环成功的报告。通过改进电解质润湿性,采用涂有铝粉的铝箔“Al@Al”,无需对支撑表面化学或电解质添加剂进行任何改性,即可实现无枝晶的电镀/剥离。无储库的Al@Al半电池在0.5 mA cm下1000次循环(1950小时)时稳定,循环库仑效率为98.9%,过电位为0.085 V。预钾化电池在很宽的电流范围内稳定,包括在3.0 mA cm下130次循环(2600分钟),过电位为0.178 V。Al@Al被4 m双(氟磺酰)亚胺钾 - 二甲氧基乙烷电解质完全润湿(θ = 0°),在初始恒电流形成循环期间产生均匀的固体电解质界面(SEI)。在具有几乎相同表面氧化物的平面铝箔上,电解质润湿性很差(θ = 52°)。这与形成时粗糙不规则的SEI团块、电镀/剥离期间具有进一步SEI粗化的三维钾岛、剥离表面上可能的死钾金属以及快速失效相关。Al@Al相对于平面Al的电化学稳定性与热润湿实验获得的亲钾性差异(几乎相同)无关。平面铜箔的电解质润湿性也很差并会形成枝晶。关键的基本要点是集流体的电解质不完全润湿会导致SEI不稳定和枝晶的早期出现。