基于聚乙烯醇的水凝胶电解质制备及其在锌碘电池性能研究

       水系锌碘电池（Aqueous zinc-iodine batteries, AZIBs）因其高安全性、元素来 源丰富和成本低等优点而受到了广泛的关注。然而，传统的 AZIBs 通常采用玻璃 纤维多孔隔膜搭配锌盐电解液，这一体系无法很好地抑制锌负极枝晶、析氢反应 以及碘正极的穿梭效应，造成不可逆的容量损失，导致电池稳定性和循环寿命降 低，严重阻碍了 AZIBs 的发展。相比之下，水凝胶电解质具有更高的机械强度和 更低的自由水含量，同时利用结构设计可优化锌离子传输速率，能够缓解上述问 题，整体提高 AZIBs 的稳定性，并促进锌碘电池的柔性应用。

       为了解决锌碘电池以上关键问题，本研究采用具有良好的机械性能、亲水性 和低成本的聚乙烯醇（Polyvinyl alcohol，PVA）制备水凝胶电解质。本研究通过 冷冻铸造技术开发的一种具有高取向结构的 PVA 基水凝胶电解质（O||-PVA/PAA）， 其沿离子传输方向的高取向液相通道加快了锌离子传输，导致了 O||-PVA/PAA 的 高离子电导率（2.32 mS cm^-1）、锌离子迁移数（0.45）及 AZIBs 优异的倍率性能。 高取向液相通道的构建还缓解了锌离子非均匀传输问题，基于 O||-PVA/PAA 的 Zn/Zn 对称电池可在 0.5 mA cm^-2 电流密度下稳定循环超 1000 小时。此外，基于 O||-PVA/PAA 的 AZIBs 可在 5 A g ^-1大电流下循环 27000 次，容量保持率高达 94.8%。

       同时，本研究结合静电纺丝和浇筑方法开发了一种聚合物互穿网络结构的 PVA 基水凝胶电解质（IN-PVA/PAN）。由于互穿网络的致密结构，IN-PVA/PAN 表现出良好的机械强度（断裂应力为 2.00 MPa），可抑制锌枝晶生长，因此，基 于IN-PVA/PAN 的Zn/Zn对称电池在1 mA cm^-2电流密度下稳定循环接近700小时。 IN-PVA/PAN 的氰基（-CN）可与多碘离子络合，从而阻碍多碘离子的穿梭效应， 因此，组装的 AZIB 自放电现象得到缓解，在 0.5 C 小倍率下库伦效率大于 90.8%。 此外，IN-PVA/PAN组装的AZIB在4 C倍率下循环2500次容量保持率高达95.9%。

       相比传统隔膜和电解液体系，O||-PVA/PAA 和 IN-PVA/PAN 均大幅提升了 AZIBs 的循环稳定性。本研究为进一步开发可整体提升 AZIB 性能的水凝胶电解质 提供了有效的结构设计策略。

Aqueous zinc-iodine batteries (AZIBs) have attracted widespread attention due to their high safety, abundant elemental sources and low cost. However, the traditional AZIBs usually uses glass fiber porous membrane (GF) with zinc salt electrolyte, which can not effectively inhibit the zinc dendrites, hydrogen evolution reaction and the shuttle effect of iodine electrode. It leads to irreversible capacity loss, resulting in limited battery stability and cycle life, seriously hindering the development of AZIBs. In contrast, hydrogel electrolytes exhibiting higher mechanical strength and lower free water content. In addition, hydrogel electrolytes can achieve high zinc ion transport rate by optimizing structural design. Hence, hydrogel electrolytes can alleviate the above problems, improve the overall stability of AZIBs and promote the flexible application of zinc-iodine batteries.

In order to solve the above key problems of zinc-iodine battery, this study used Polyvinyl alcohol (PVA) to prepare hydrogel electrolyte，owing to good mechanical properties, hydrophilicity and low cost of PVA. In this work, a PVA-based hydrogel electrolyte (O||-PVA/PAA) with a highly orientated structure was developed by freeze casting technology. Its highly orientated liquid phase channel along the ion transport direction accelerated zinc ion transport. Hence, the high ionic conductivity (2.32 mS cm^-1 ), zinc ion migration number (0.45) of O||-PVA/PAA and excellent magnification performance of AZIB were obtained. The construction of high orientation liquid phase channel also ameliorates the problem of non-uniform transmission of zinc ions. Therefore, Zn/Zn-symmetric battery based on O||-PVA/PAA can cycle stably for more than 1000 hours at 0.5 mA cm^-2 current density. Besides, AZIBs based on O||-PVA/PAA cycled 27000 times at 5 A g ^-1 current with high capacity retention rate of 94.8%.

In this work, a PVa-based hydrogel electrolyte (IN-PVA/PAN) with polymer interpenetrating network structure was developed by combining electrospinning and pouring methods. Due to the dense structure of the interpenetrating network, IN-PVA/PAN exhibits good mechanical strength (the breaking stress is 2.00 MPa). The electrolyte with high mechanical strength can inhibit the growth of zinc dendrite, owing to which the Zn/Zn battery based on IN-PVA/PAN has a stable cycle of nearly 700 h at 1 mA cm^-2 current. The cyanide group (-CN) of IN-PVA/PAN can be complex with polyiodide ions, preventing the shuttle of polyiodide ions. Therefore, the self-discharge phenomenon of AZIB is alleviated, in result of which the coulomb efficiency is greater than 90.8% at a small rate of 0.5 C. Besides, AZIBs assembled by IN-PVA/PAN exhibited a capacity retention rate of 95.9% at a 4 C ratio after 2500 cycles.

Compared with traditional GF (using aqueous electrolyte), both O||-PVA/PAA and IN-PVA/PAN greatly improved the cyclic stability of AZIBs, showing excellent capacity retention rate after a long period of charge and discharge cycles. This study provides an effective structural design strategy for further developing hydrogel electrolytes to improve the performance of AZIBs.

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