先进钠金属负极的界面设计及电化学性能研究

    金属钠具有高比容量（1166.00 mAh g^-1）和丰富的储量，是实现高能量密度钠电池最理想的负极材料。然而，由于初始不均匀的钠成核以及不稳定的固体电解质界面膜（SEI），钠金属负极在循环过程中面临钠枝晶生长、电池库仑效率低以及安全性等问题，极大地限制了其商业应用。以上问题和钠金属负极与电解液间固液界面的反应息息相关。因此，本论文聚焦钠金属负极的电化学界面，通过负极界面集流体设计和电解液化学优化等策略，探讨了调控钠成核/生长，以及SEI性质的方法和相关机理，从而达到钠金属负极在可充放电电池中长期稳定性的目标，具体研究如下：

    首先，本研究通过简单的化学镀方法，设计了一种亲钠性缓冲Cu₆Sn₅合金层用于负极基底界面，调控钠成核/生长行为。该合金层的界面设计既能有效地提高商用铜箔基底的亲钠性，有助于均匀钠沉积。同时可以作为缓冲层，显著释放了合金反应引起的内应力和缓解负极体积变化，抑制了合金层的剥落。基于这些协同效应，在80%的超高放电深度时，Cu₆Sn₅@Cu集流体表现出600小时的稳定性能，实现了可大规模生产且满足深度充放电的长寿命钠金属负极集流体。

    除了负极界面设计，本研究还通过调控电解液配方（引入15-冠醚-5添加剂）改善钠成核/生长，以及SEI界面化学。具体来说，理论计算和实验研究表明15-冠醚-5添加剂通过与钠离子形成强配位作用，导致了减缓的去溶剂化动力学和阴离子富集的溶剂化结构，进而实现了均匀的成核，并构建了快离子传导和高机械性能的SEI。因此，15-冠醚-5添加剂实现了稳定循环超过1年的钠金属负极（库仑效率高达99.95%），其优异的电化学性能超过了近年来大部分的研究成果。

    为了进一步探究电解液组分对于钠金属负极界面化学与钠枝晶生长的影响，本研究利用不同浓度（0.5 M-2.5 M）的经典NaPF₆-二乙二醇二甲醚电解液体系为模型，系统地阐明了电解液浓度、桑德时间（Sand's time）和SEI之间的平衡关系。研究表明低浓度会造成短的桑德时间和脆弱的SEI，但是过高浓度又无法维持钠均匀生长和SEI的平衡关系，均不利于钠金属负极稳定运行。因此，在中等浓度（2.0 M）的电解液中，钠金属负极取得了最佳的电化学性能：既有长的桑德时间，延缓枝晶的形成，又生成了无机组分为主的SEI，抑制枝晶的生长。最终得到电解液化学、成核/生长行为和SEI性质之间的关系，为未来电解液的设计提供了理论指导。

  Sodium (Na) metal possessing abundant reserves and a high specific capacity of 1166.00 mAh g^-1, is the ideal anode for high energy density Na batteries. However, its practical application is hindered by many issues, including initially uneven Na nucleation and unstable solid electrolyte interphase (SEI), giving rise to dendrite growth, low Coulombic efficiency, and safety concerns. These issues are closely related to the solid-liquid interphase reactions between Na metal anodes and electrolytes. Therefore, this thesis focuses on electrochemical interphase to discuss the methods and related mechanisms of regulating Na nucleation/growth and SEI properties via metal anode interphase design and electrolyte formulation optimization strategies, achieving long-term stable Na metal batteries. The details are as follows:

  First, we design a sodiophilic/buffered Cu₆Sn₅ alloy layer on anode substrate interphase to manipulate Na nucleation/growth behavior by a facile electroless plating method. Such interphase design of the alloy layer significantly enhances the commercial Cu substrate's sodiophilicity, conducive to uniform Na deposition. On the other hand, it acts as a buffer layer, greatly releasing the internal stress caused by the alloy reaction and alleviating volume change, which prevents the peeling of alloy layer. Based on these synergetic effects, the easy scale-up Cu₆Sn₅@Cu current collector achieves 600 h lifetime under an ultrahigh depth of discharge (80%).

  Apart from anode interphase design, the electrolyte recipe regulation (i.e., introducing 15-crown-5 additive) is proposed to optimize Na nucleation/deposition and SEI chemistry. Specifically, theoretical calculations and experimental investigations indicate 15-crown-5 additive 's strong complexation ability with Na⁺ leads to slower desolvation kinetics and anion-rich solvation sheath, resulting in even nucleation and high ionic conductivity/mechanical property SEI. Therefore, a high average Coulombic efficiency of 99.95% beyond one year is realized, surpassing most previous studies.

  To further investigate the effects of electrolyte components on anode interfacial chemistry and sodium dendrite growth, a classic NaPF₆-diethylene glycol dimethyl ether electrolyte system with different concentrations (0.5 M-2.5 M) is employed as a model to systematically elucidate the equilibrium relationship between electrolyte concentration, Sand's time and SEI. It is found that low concentration causes short Sand’s time and frail SEI, but overly high one cannot maintain the balance between dendrite growth and SEI, which are detrimental to the stable operation of Na metal anodes. As a result, the optimal electrochemical performance is achieved at 2.0 M electrolyte owing to its long Sand's time and inorganic composition-occupied SEI, which delay dendrites formation and suppress their growth. These findings reveal the relationship among electrolyte chemistry, nucleation/growth behavior and SEI properties, which provides a theoretical guideline for future electrolyte design.

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