Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China.
Nat Commun. 2016 Jun 20;7:11982. doi: 10.1038/ncomms11982.
Rechargeable aqueous metal-ion batteries made from non-flammable and low-cost materials offer promising opportunities in large-scale utility grid applications, yet low voltage and energy output, as well as limited cycle life remain critical drawbacks in their electrochemical operation. Here we develop a series of high-voltage aqueous metal-ion batteries based on 'M(+)/N(+)-dual shuttles' to overcome these drawbacks. They utilize open-framework indium hexacyanoferrates as cathode materials, and TiP2O7 and NaTi2(PO4)3 as anode materials, respectively. All of them possess strong rate capability as ultra-capacitors. Through multiple characterization techniques combined with ab initio calculations, water-mediated cation intercalation of indium hexacyanoferrate is unveiled. Water is supposed to be co-inserted with Li(+) or Na(+), which evidently raises the intercalation voltage and reduces diffusion kinetics. As for K(+), water is not involved in the intercalation because of the channel space limitation.
可充电的水系金属离子电池由不易燃且低成本的材料制成，在大规模的公共电网应用中具有广阔的前景，然而低电压和能量输出，以及有限的循环寿命仍然是其电化学运行的关键缺陷。在这里，我们开发了一系列基于“M(+)/N(+)-双重穿梭”的高压水系金属离子电池来克服这些缺点。它们分别使用开架式亚铁氰化铟作为正极材料，和 TiP2O7 和 NaTi2(PO4)3 作为负极材料。它们都具有作为超级电容器的强大倍率性能。通过结合从头算计算的多种表征技术，揭示了水介导的亚铁氰化铟中的阳离子插层。水应该与 Li(+)或 Na(+)共同插入，这显然会提高插层电压并降低扩散动力学。对于 K(+)，由于通道空间的限制，水不参与插层。
