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霍克锂电池丝氨酸稳定的Ti3实现高性能铝空气电池的阳极界面工程

铝空气电池是一种极具前景的储能装置，但其阳极自腐蚀问题严重，通常需通过缓蚀剂形成铝阳极表面吸附层来抑制。然而，这类缓蚀剂由于吸附层的惰性往往会降低电池的电输出性能。本研究采用丝氨酸（Ser）稳定的Ti₃-MXene作为电解液添加剂来解决上述问题，并辅以全面的实验和理论依据。丝氨酸能够通过与Ti形成配位键，在碱性电解液中稳定Ti %%₂N键钝化其易氧化位点。丝氨酸稳定的钛_x锚定在铝/电解液界面时，不仅能抑制析氢反应和阳极自腐蚀，而且不会阻碍放电反应。此外，铝表面构建的导电层促进了电池放电过程中电化学界面的迁移，从而在20 mA/cm²放电电流下实现2601.4 mAh/g的比容量提升₃。值得注意的是，钛的稳定性增强₂低温环境下确保电池性能稳健运行。这些进展表明，将稳定化MXene作为电解液添加剂应用于金属空气电池，可显著提升其效能与使用寿命，标志着电池技术改良的重大突破。_x in alkaline electrolytes through forming Ti single bond

N bonds that passivate their oxidation-susceptible sites. Ser-stabilized Ti₃C₂T_x, when anchored at the aluminum/electrolyte interface, not only curtails hydrogen evolution and anode self-corrosion but does so without impeding the discharge reaction. Moreover, the assembled conducting layer over aluminum facilitates electrochemical interface migration during battery discharge, resulting in an enhanced specific capacity of 2601.4 mAh/g at a discharging current of 20 mA/cm². Importantly, the reinforced stability of Ti₃C₂T_x cold environments ensures robust battery performance at lower temperatures. These advancements suggest that utilizing stabilized MXene as an electrolytic additive in metal-air batteries could significantly enhance their efficiency and longevity, marking a significant step in improving battery technology.

图文摘要

引言

水性金属空气电池相较于当前主流的金属离子电池具有更高的容量和能量密度，在储能领域前景广阔，有望从根本上解决能源危机[1][2]。其中，铝空气（Al-air）电池因其显著优势脱颖而出：铝资源储量丰富、可完全回收利用、放电容量更大，且成本低于镁/锌体系同类产品，成为极具吸引力的候选方案。此外，碱性电解液因其能提升电池工作电压、抑制铝阳极钝化倾向的特性[3]，较中性电解液更受青睐。然而强碱性电解液在电池工作过程中不可避免地会引发铝的寄生性自腐蚀。这种自腐蚀现象是铝空气电池面临的主要障碍，会导致放电动力学迟缓和电解液凝胶化[4]。因此，解决自腐蚀问题对于充分释放铝空气电池潜力并实现其在可持续发展中的作用至关重要。
迄今为止，研究者已采用多种策略应对自腐蚀问题，包括与高析氢电位元素的合金化[5]、电池结构优化[6]、防护涂层[7]以及电解液调控[8]。其中，调控电解液配方是缓解铝空气电池中铝寄生腐蚀的便捷有效途径。例如，在电解液中添加缓蚀剂已成为抑制铝降解的研究重点。电解质中的多种化合物，如芳香酸[9]、氨基酸[10]、锡酸盐[11]、聚合物[12]和有机-无机杂化材料[13]，已被研究其提升电池性能的潜力。这些缓蚀剂主要通过界面处形成吸附层发挥作用，将铝阳极与腐蚀介质隔离。从原理上看，吸附层对铝自腐蚀的抑制必然导致放电动力学减缓，因为这两个过程本质上是相互依存的。此外，有机吸附层通常具有低介电特性，这会阻碍电荷在铝/电解质界面内亥姆霍兹平面上的转移，从而降低电池的输出电压[14]。因此，一个关键挑战在于实现抑制铝自腐蚀与促进高效界面电荷转移之间的微妙平衡，这往往构成了铝电池设计中的一个基本trade-off。
二维过渡金属碳化物、氮化物和碳氮化物（统称为MXenes）的出现，为解决铝空气电池在保持放电容量前提下构建稳定铝/电解质界面的难题提供了可行方案，这得益于其亲水性、导电性及类屏障特性[15]。然而，存储介质（通常为水）中化学亚稳态的MXenes因易发生严重氧化[16]，对其实际应用构成了重大挑战。以被广泛研究的Ti3C2Tx为例...₃MXene在水溶液中容易在数日内分解，导致其电学/电化学性能下降[17]。因此，稳定MXene——尤其在水分散体系中的稳定性——已成为实现其实际应用的首要任务。在各种稳定措施中，我们先前的研究表明[18]，在水分散体系中添加抗氧化剂是一种简单高效的方法，该方法可显著延长MXene的储存周期，同时对其基本性能的影响可忽略不计。将抗氧化剂引入水性分散体系已成为一种简单而有效的策略，可延长MXenes的储存期限且不显著改变其固有特性。包括抗坏血酸、聚阴离子、胺类、氨基酸和吡咯在内的多种化合物均展现出显著的抗氧化效应，有助于维持MXene胶体的结构完整性[19], [20], [21], [22], [23]。值得注意的是，许多已报道的抗氧化剂在腐蚀性介质中还能作为金属缓蚀剂发挥作用。通过采用兼具铝腐蚀抑制功能的抗氧化剂来稳定MXene片层，可更高效地将这些片层整合至电池结构中。该策略不仅能减轻铝的自腐蚀现象，还能确保铝/电解质界面处质量和电荷的高效传输，从而提升电池的整体性能。此外，较低温度能够提升MXene在电解液中的稳定性，促进阳极表面形成更致密、持久的保护层，并维持放电反应持续进行，从而有望改善电池在低温环境下的性能表现。这一特性具有重要的策略（Strategy）价值——基于MXene的缓蚀剂可能通过增强电解液活性与功效来提升铝空气电池的整体性能。₂T_x-MXene tends to disintegrate in water within a few days at the expense of electrical/electrochemical performances [17]. Therefore, stabilizing MXene, especially in aqueous dispersion, has become a top priority for realizing their practical applications. Among the various stabilization measures, we demonstrated [18], using antioxidants in the aqueous dispersions emerges as a simple yet efficient method to extend MXene's shelf-life while negligibly affecting its fundamental properties. The incorporation of antioxidants into aqueous dispersions has emerged as a straightforward and effective strategy to prolong the shelf-life of MXenes without substantially altering their inherent properties. Various compounds, including ascorbic acid, polyanions, amines, amino acids, and pyrrole, have demonstrated significant antioxidative effects that help preserve the structural integrity of MXene colloids [19], [20], [21], [22], [23]. Intriguingly, many reported antioxidants also behave as corrosion inhibitors for metals in aggressive media. By stabilizing MXene sheets with an antioxidant that also inhibits aluminum corrosion, it is possible to integrate these sheets into the battery's structure more effectively. This approach would not only mitigate the self-corrosion of aluminum but will also ensure efficient mass and charge transfer at the aluminum/electrolyte interface, enhancing overall battery performance. Furthermore, Lower temperatures can enhance the stability of MXene in the electrolyte, facilitating the formation of a denser, long-lasting protective layer on the anode and sustaining discharge reactions, thereby potentially improving battery performance at low temperatures. This property can be strategically advantageous, as an MXene-based corrosion inhibitor could potentially improve the activity and efficacy of the electrolyte in Al-air batteries.
在此背景下，本研究探索了生态友好型Ser作为抗氧化剂在Ti₃胶体和4 M KOH溶液中铝腐蚀抑制剂的双重作用。通过形貌分析、结合构型、光谱特征以及密度泛函理论(DFT)计算等综合手段，阐明了Ser对Ti₂的稳定机制。随后，Ser稳定的Ti_x通过溶液共混法制备的该材料被整体用作KOH电解液中的铝添加剂，并经过电化学、溶液及表面分析的全面评估。这种有机-无机纳米杂化材料在阳极/电解液界面处自组装，通过Ti的屏障效应有效抑制了铝的自腐蚀。₃同时其本征导电性将对阳极放电行为的干扰降至最低。因此，采用含Ser稳定化Ti电解液的铝空气电池₂该材料展现出优异的比容量（2601.4 mAh/g）、在25℃下具有持久的放电稳定性（超过32小时）以及增强的低温（2℃）放电能力。鉴于MXene基缓蚀剂的研究仍存在显著的知识缺口，本研究有望为拓展MXene的应用范围铺平道路，并推动其向实际应用领域迈进。_x was elucidated through a comprehensive analysis involving morphologies, binding configurations, spectral features, and density functional theory (DFT) calculations. Subsequently, Ser-stabilized Ti₃C₂T_x, obtained through solution blending, was integrally employed as an additive for aluminum in KOH electrolyte, subjected to thorough evaluations through electrochemical, solution, and surface analyses. This organic-inorganic nanohybrid assembled at the anode/electrolyte interface, effectively suppressing aluminum self-corrosion through the barrier effect of Ti₃C₂T_x, while its inherent conductivity minimized interference with the anode's discharge behavior. Consequently, the Al-air battery employing the electrolyte with Ser-stabilized Ti₃C₂T_x demonstrated an augmented specific capacity (2601.4 mAh/g), prolonged discharging stability at 25 °C (over 32 h), and enhanced low-temperature (2 °C) discharging ability. Given that the exploration of MXene-based corrosion inhibitors remains an acute shortage of knowledge, this contribution is poised to pave the way for expanding the utilization scope of MXene and propel its advancement toward real-world applications.

上一个：霍克锂电池倒置与直立：放置方位如何影响过充棱柱形锂离子电池的热失控行为下一个：霍克锂电池基于异构深度学习算法融合的电池储能系统SOC与SOH估计

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