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Regulation of Ionic Distribution and Desolvation Activation Energy Enabled by In Situ Zinc Phosphate Protective Layer toward Highly Reversible Zinc Metal Anodes
Advanced Functional Materials ( IF 19.0 ) Pub Date : 2023-03-05 , DOI: 10.1002/adfm.202208230 Shengzhao Zhang, Minghui Ye, Yufei Zhang, Yongchao Tang, Xiaoqing Liu, Cheng Chao Li
Advanced Functional Materials ( IF 19.0 ) Pub Date : 2023-03-05 , DOI: 10.1002/adfm.202208230 Shengzhao Zhang, Minghui Ye, Yufei Zhang, Yongchao Tang, Xiaoqing Liu, Cheng Chao Li
Despite the merits of high specific capacity, low cost, and high safety, the practical application of aqueous Zn metal batteries (AZMBs) is plagued by the dendritic growth and corrosion reaction of Zn metal anodes. To solve these issues, a Zn3(PO4)2·4H2O protective layer is in-situ constructed on Zn foil (Zn@ZnPO) by a simple hydrothermal method, avoiding the traditional slurry-casting process. The insulating and conformable ZnPO layer improves the wettability of Zn@ZnPO and aqueous electrolyte via decreasing the contact angle to 11.7o. Compared with bare Zn, the Zn@ZnPO possesses a lower desolvation activation energy of 35.25 kJ mol-1, indicating that the ZnPO fasters the desolvation of hydrated Zn2+ ions and thereby ameliorates their transport dynamics. Micro-morphology and structural characterization show that there are no dendrites forming on the post-cycling Zn@ZnPO anodes, and the interfacial ZnPO layer remains almost identical before and after cycles. It can be explained that the electrochemically stable ZnPO layer acts as an ionic modulator to enable the homogeneous distribution of Zn2+ ions, inhibiting the growth of Zn dendrites. Benefiting from these advantages, the Zn@ZnPO based symmetric and full cells deliver highly reversible Zn plating/stripping behavior and long cycling lifespans.
中文翻译:
原位磷酸锌保护层对高度可逆锌金属阳极离子分布和去溶剂化活化能的调控
尽管具有高比容量、低成本和高安全性等优点,但水系锌金属电池(AZMBs)的实际应用受到锌金属负极的枝晶生长和腐蚀反应的困扰。为了解决这些问题,采用简单的水热法在锌箔(Zn@ZnPO)上原位构建Zn 3 (PO 4 ) 2 ·4H 2 O保护层,避免了传统的浆料浇铸工艺。绝缘且贴合的 ZnPO 层通过将接触角降低至 11.7 °来提高 Zn@ZnPO 和含水电解质的润湿性。与裸锌相比,Zn@ZnPO 具有较低的去溶剂化活化能,为 35.25 kJ mol -1,表明 ZnPO 加快了水合 Zn 2+离子的去溶剂化作用,从而改善了它们的传输动力学。微观形貌和结构表征表明,循环后的 Zn@ZnPO 负极上没有形成枝晶,界面 ZnPO 层在循环前后几乎保持相同。可以解释为电化学稳定的 ZnPO 层充当离子调节剂,使 Zn 2+离子均匀分布,抑制锌枝晶的生长。受益于这些优势,基于 Zn@ZnPO 的对称和全电池具有高度可逆的镀锌/剥离行为和长循环寿命。
更新日期:2023-03-05
中文翻译:
原位磷酸锌保护层对高度可逆锌金属阳极离子分布和去溶剂化活化能的调控
尽管具有高比容量、低成本和高安全性等优点,但水系锌金属电池(AZMBs)的实际应用受到锌金属负极的枝晶生长和腐蚀反应的困扰。为了解决这些问题,采用简单的水热法在锌箔(Zn@ZnPO)上原位构建Zn 3 (PO 4 ) 2 ·4H 2 O保护层,避免了传统的浆料浇铸工艺。绝缘且贴合的 ZnPO 层通过将接触角降低至 11.7 °来提高 Zn@ZnPO 和含水电解质的润湿性。与裸锌相比,Zn@ZnPO 具有较低的去溶剂化活化能,为 35.25 kJ mol -1,表明 ZnPO 加快了水合 Zn 2+离子的去溶剂化作用,从而改善了它们的传输动力学。微观形貌和结构表征表明,循环后的 Zn@ZnPO 负极上没有形成枝晶,界面 ZnPO 层在循环前后几乎保持相同。可以解释为电化学稳定的 ZnPO 层充当离子调节剂,使 Zn 2+离子均匀分布,抑制锌枝晶的生长。受益于这些优势,基于 Zn@ZnPO 的对称和全电池具有高度可逆的镀锌/剥离行为和长循环寿命。