Ultrafast Resonance Raman Characteristics of Sodium Polysulfides in Sodium-Sulfur Battery: An ab initio Assessment

doi:10.6023/A25090312

Abstract

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

Cite this article

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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Fig. & Tab. 5

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

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

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)

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

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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