The construction of aqueous rechargeable ammonium-iodine batteries (AIBs) must be eye-catching by combining the unique properties of ammonium ion (NH₄⁺) and the special redox mechanism of iodine. Polyaniline (PANI) as a conductive polymer is a potential cathode material for aqueous NH₄⁺ batteries. However, the proton (H⁺) escape of amino group (─NH─) in the oxidation process of PANI cannot realize the reversible reduction reaction from full-oxidized imine (─N═) to ─NH─. In this work, polyaniline with H⁺ reservoirs (PANI-H⁺) was successfully prepared by electrodeposition for the NH₄⁺ and I₃⁻/I₂ storage. Interestingly, ─SO₃⁻H⁺ groups as H⁺ reservoirs in 1, 5-Naphthalenedisulfonic acid (1, 5-NDSA) can provide H⁺ for the reduction of ═N─ to ─NH─, thus achieving the reversible redox process of PANI-H⁺. Therefore, PANI-H⁺ electrode exhibited excellent discharge capacity (299.3 mAh/g and 126.7mAh/g at the current density of 1 A/g and 10 A/g, respectively), and good stability of long-term cycles (≈100 % capacity retention after 1000 cycles at the current density of 10 A/g) in (NH₄)₂SO₄ + I₃⁻ electrolyte. A series of spectroscopy analyses indicated the dual storage mechanism of NH₄⁺ (de)intercalation and interfacial redox of I₃⁻/I₂. Finally, aqueous ammonium-iodine full cell (PTCDA|(NH₄)₂SO₄ + I₃⁻|PANI-H⁺) was constructed and presented satisfactory electrochemical performances. This work provides guidance to construct promising AIBs.

中文翻译：

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一种带有 H+ 储墨槽的聚苯胺，用于双机制 NH4+ 和 I3−/I2 储存


结合铵离子 （NH₄⁺） 的独特特性和碘的特殊氧化还原机制，水性可充电铵碘电池 （AIB） 的结构必须引人注目。聚苯胺 （PANI） 作为一种导电聚合物，是一种用于 NH₄⁺ 水性电池的潜在阴极材料。然而，在PANI的氧化过程中，氨基（─NH─）的质子（H⁺）逃逸无法实现从完全氧化的亚胺（─N═）到─NH─的可逆还原反应。在本工作中，通过电沉积成功制备了具有 H⁺ 储层的聚苯胺 （PANI-H⁺），用于 NH₄⁺ 和 I₃⁻/I₂ 储存。有趣的是，─SO₃⁻H⁺ 基团作为 1,5-萘二磺酸 （1， 5-NDSA） 中的 H⁺ 储层可以提供 H⁺ 用于将 ═N─ 还原为 ─NH─，从而实现 PANI-H⁺ 的可逆氧化还原过程。因此，PANI-H⁺ 电极在 （NH₄）₂SO₄ + I₃⁻ 电解液中表现出优异的放电容量（在 1 A/g 和 10 A/g 的电流密度下分别为 299.3 mAh/g 和 126.7mAh/g）和良好的长期循环稳定性（在 10 A/g 的电流密度下循环 1000 次后容量保持 ≈100 %）。一系列光谱分析表明 NH₄⁺（脱）插层和 I₃⁻/I₂ 界面氧化还原的双重存储机制。 最后，铵碘水全细胞 （PTCDA|（NH₄）₂SO₄ + I₃⁻|PANI-H⁺） 构建并呈现出令人满意的电化学性能。这项工作为构建有前途的 AIB 提供了指导。