Zhang Xiaoqin, Chen Ji, Cao Heng, Huang Xiaomin, Liu Yu, Chen Yuxiang, Huo Yu, Lin Dunmin, Zheng Qiaoji, Lam Kwok-Ho
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu, 610066, China.
Centre for Medical and Industrial Ultrasonics, James Watt School of Engineering, University of Glasgow, Glasgow, Scotland, G12 8QQ, United Kingdom.
Small. 2023 Dec;19(52):e2303906. doi: 10.1002/smll.202303906. Epub 2023 Aug 30.
Aqueous zinc-ion batteries (AZIBs) have attracted considerable attention due to their low cost and environmental friendliness. However, the rampant dendrite growth and severe side reactions during plating/stripping on the surface of zinc (Zn) anode hinder the practicability of AZIBs. Herein, an effective and non-toxic cationic electrolyte additive of Rb SO is proposed to address the issues. The large cation of Rb is preferentially adsorbed on the surface of Zn metal to induce a strong shielding effect for realizing the lateral deposition of Zn ions along the Zn surface and isolating water from Zn metal to effectively inhibit side reactions. Consequently, the Zn||Zn symmetric cell with the addition of 1.5 mm Rb SO can cycle more than 6000 h at 0.5 mA cm /0.25 mAh cm , which is 20 times longer than that without Rb SO . Besides, the Zn||Cu asymmetric cell with Rb SO achieves a very high average Coulombic efficiency of 99.16% up to 500 cycles. Moreover, the electrolyte with Rb SO well matches with the VO cathode, achieving high initial capacity of 412.7 mAh g at 5 A g and excellent cycling stability with a capacity retention of 71.6% at 5 A g after 500 cycles for the Zn//VO full cell.
水系锌离子电池(AZIBs)因其低成本和环境友好性而备受关注。然而,锌(Zn)阳极表面在电镀/剥离过程中枝晶生长猖獗且副反应严重,阻碍了水系锌离子电池的实用性。在此,提出了一种有效且无毒的阳离子电解质添加剂Rb₂SO₄来解决这些问题。Rb⁺大阳离子优先吸附在Zn金属表面,诱导出强烈的屏蔽效应,以实现Zn离子沿Zn表面的横向沉积,并将水与Zn金属隔离,从而有效抑制副反应。因此,添加1.5 mM Rb₂SO₄的Zn||Zn对称电池在0.5 mA cm⁻²/0.25 mAh cm⁻²下可循环超过6000小时,这比不添加Rb₂SO₄的情况长20倍。此外,含有Rb₂SO₄的Zn||Cu不对称电池在500次循环内实现了高达99.16%的非常高的平均库仑效率。而且,含有Rb₂SO₄的电解质与VO₂正极匹配良好,对于Zn//VO₂全电池,在5 A g⁻¹时实现了412.7 mAh g⁻¹的高初始容量,以及在5 A g⁻¹下500次循环后容量保持率为71.6%的优异循环稳定性。