钠硫电池中多硫化钠中间产物超快共振拉曼特征信号的理论解析

doi:10.6023/A25090312

摘要/Abstract

钠硫电池作为极具潜力的储能装置, 其发展长期受能量转化过程中穿梭效应的制约. 工作状态的钠硫电池内部存在多个级联的氧化还原反应, 产物为多种溶于电解质溶液的钠硫化合物. 各类多硫化钠中间体在正负极间的扩散迁移是穿梭效应的主导因素. 目前关于穿梭效应的微观机制, 包括导致活性物质流失的具体化学物种及其氧化还原反应动力学机理仍不明确. 由于多硫化钠具有极快的反应动力学和高度动态的结构演化行为, 传统表征手段难以表征其瞬态过程. 本工作基于高精度量子化学从头计算, 研究了多种多硫化钠中间产物的共振拉曼和超快共振拉曼光谱. 结合了共振拉曼光谱在化学键尺度上的空间分辨能力和超快光谱在飞秒尺度上的时间分辨能力, 具备在钠硫电池工作过程中捕捉多硫化钠光谱特征的潜力. 计算结果表明, 不同多硫化钠中间体的共振拉曼信号同时具有激发波长选择性和电子振动耦合选择性, 其特征显著、易于区分. 本工作为多硫化钠中间体的高时空分辨、实时及原位表征提供了理论依据和参考, 为穿梭效应理论机制的研究提供借鉴.

关键词: 钠硫电池, 共振拉曼, 超快光谱, 多硫化钠, 穿梭效应

Sodium-sulfur batteries (NaSBs) are promising alternative to lithium-sulfur batteries due to their high theoretical energy density, low cost, and abundant raw materials. However, their practical development is significantly hindered by the polysulfide shuttle effect. This effect arises from soluble sodium polysulfide (NaPS) intermediates formed during cycling, which migrate between electrodes, causing irreversible sulfur loss and rapid capacity fade. Understanding the specific chemical species of these NaPS intermediates and their rapid reaction dynamics is essential for mitigating the shuttle effect and improving battery stability. Unfortunately, conventional analytical techniques lack the temporal resolution to capture the fast structural changes and reaction kinetics involved. To address this challenge, we propose utilizing ultrafast resonance Raman spectroscopy. Spontaneous resonance Raman (spRR) significantly enhances detection sensitivity for target molecules by matching the excitation light frequency to specific electronic transitions. By employing ultrafast broadband laser pulses, this approach can be extended to stimulated resonance Raman (stRR), achieving the necessary femtosecond time resolution to track NaPS evolution with high selectivity and spatial-temporal precision. Through high-accuracy ab initio quantum chemical calculations, we calculate and analyze the resonance Raman spectral signatures of key NaPS intermediates. Our results reveal distinct spectral fingerprints and their selective enhancement under specific excitation energies. These insights provide a deeper understanding of NaPS conversion dynamics and establish a foundation for real-time, in-situ monitoring of polysulfide species during battery operation. This work advances the fundamental knowledge required to develop efficient and stable NaSBs for future energy storage.

Key words: sodium-sulfur battery, resonance raman, ultrafast spectroscopy, sodium polysulfides, shuttle effect

引用此文

赵宝国, 李展, 马慧芳, 任浩. 钠硫电池中多硫化钠中间产物超快共振拉曼特征信号的理论解析[J]. 化学学报, 2026, 84(2): 214-222.

Baoguo Zhao, Zhan Li, Huifang Ma, Hao Ren. Ultrafast Resonance Raman Characteristics of Sodium Polysulfides in Sodium-Sulfur Battery: An ab initio Assessment[J]. Acta Chimica Sinica, 2026, 84(2): 214-222.

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图/表 5

图1. NaPSs稳定结构示意图. 紫色、黄色球体分别表示Na原子和S原子. 化学键旁数字为键长(单位: nm)

Figure 1. Optimized structures of NaPSs. Purple and yellow balls represent sodium and sulfur atoms, respectively. Typical bond lengths (in nm) were labeled

图2. Na2S2至Na2S8的振动分辨的紫外-可见吸收光谱. 总吸收(total absorption, ToT)光谱以黑色曲线表示; 对吸收贡献显著的电子激发态以εi标注, 其中εi表示该体系中的第i个电子跃迁过程

Figure 2. Vibration-resolved UV-vis absorption spectra of Na2S2~Na2S8. The total absorption (ToT) spectra are plotted in black. Electronic excitations with remarkable contributions are labeled by εi, representing the i-th electronic transition in each system

图3. Na2S2至Na2S8的二维自发共振拉曼光谱[图(a)~(f)]. 图中横轴表示拉曼位移, 对应于体系的分子振动模式, 单位为波数(单位: cm−1); 纵轴表示激发光子的能量, 激发能量范围20,000至40,000 cm−1; 右侧色条表示二维图中的拉曼强度

Figure 3. Two-dimensional spRR spectrum of Na2S2~Na2S8 [(a)~(f)]. The horizontal axis represents the Raman shift, corresponding to the molecular vibrational modes of the system, in units of wavenumber (cm−1); the vertical axis indicates the excitation energy, with ranging from 20,000 to 40,000 cm−1; the color bar on the right signifies the Raman intensity in the two-dimensional maps

Na₂S_n	振动频率/cm⁻¹	振动描述
Na₂S₂	466	S—S伸缩
Na₂S₃	488	链端S伸缩
Na₂S₄	459	S2—S3伸缩
Na₂S₄	501	链端S伸缩
Na₂S₅	466	S2—S3伸缩
Na₂S₅	508	链端S伸缩
Na₂S₆	403	S3—S4伸缩
Na₂S₆	480	硫链整体伸缩
Na₂S₆	521	链端S伸缩
Na₂S₈	425	S3—S4伸缩
Na₂S₈	473	硫链整体伸缩
Na₂S₈	512	链端S伸缩(S1—S2)
Na₂S₈	520	链端S伸缩(S7—S8)

表1. Na2Sn的拉曼活性模式, 频率单位为波数(cm−1)

Table 1. Raman active modes of Na2Sn. Frequency units are expressed in wavenumbers (cm−1)

图4. Na2S2至Na2S8的spRR与stRR光谱. 实线表示spRR光谱, 虚线表示stRR光谱. 对于spRR光谱, 所选激发能量与标记为εi的电子跃迁共振; 而在stRR光谱中, 泵浦-探测脉冲对表示为(ε0, εi), 其中ε0=20,000 cm−1被设定为与特定电子跃迁预共振(pre-resonant)

Figure 4. spRR and stRR spectra of Na2S2至Na2S8. The solid curves correspond to the spRR spectra, and the dashed curves correspond to the stRR spectra. For the spRR spectra, the selected excitation energy resonates with the strong electronic transition labeled εi. For the stRR spectra, the pump-probe pulse pair is denoted as (ε0, εi), where ε0=20,000 cm−1 was set to be pre-resonant with a specific electronic transition

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