Xiao Yao, Yamamoto Kentaro, Matsui Yukiko, Watanabe Toshiki, Nakanishi Koji, Uchiyama Tomoki, Shingubara Shoso, Ishikawa Masashi, Watanabe Masayoshi, Uchimoto Yoshiharu
Graduate School of Human and Environmental Studies, Kyoto University Yoshida-nihonmatsu-cho, Sakyo-ku Kyoto 606-8501 Japan
Department of Chemistry and Materials Engineering, Kansai University 3-3-35 Yamate-cho Suita Osaka 564-8680 Japan.
RSC Adv. 2020 Nov 2;10(65):39875-39880. doi: 10.1039/d0ra08299f. eCollection 2020 Oct 27.
Sulfur is a promising material for next-generation cathodes, owing to its high energy and low cost. However, sulfur cathodes have the disadvantage of serious cyclability issues due to the dissolution of polysulfides that form as intermediate products during discharge/charge cycling. Filling sulfur into the micropores of porous carbon is an effective method to suppress its dissolution. Although microporous carbon-supported sulfur cathodes show an electrochemical behavior different from that of the conventional sulfur ones, the corresponding reaction mechanism is not clearly understood. In this study, we focused on clarifying the reaction mechanism of microporous carbon-supported sulfur cathodes by soft X-ray absorption spectroscopy. In the microporous carbon support, sulfur was present as smaller fragments compared to conventional sulfur. During the first discharge process, the sulfur species in the microporous carbon were initially reduced to S and S and then to LiS. The S and S species were observed first, with S being the main polysulfide species during the discharge process, while LiS was produced in the final discharge process. The narrow pores of microporous carbon prevent the dissolution of polysulfides and influence the reaction mechanism of sulfur cathodes.
由于硫具有高能量和低成本的特点,它是下一代阴极材料的一个有前景的选择。然而,硫阴极存在严重的循环稳定性问题,这是由于在充放电循环过程中作为中间产物形成的多硫化物会溶解。将硫填充到多孔碳的微孔中是抑制其溶解的有效方法。尽管微孔碳负载的硫阴极表现出与传统硫阴极不同的电化学行为,但其相应的反应机理尚不清楚。在本研究中,我们专注于通过软X射线吸收光谱法阐明微孔碳负载硫阴极的反应机理。在微孔碳载体中,与传统硫相比,硫以较小的碎片形式存在。在第一次放电过程中,微孔碳中的硫物种首先被还原为S和S,然后再还原为LiS。首先观察到S和S物种,S是放电过程中的主要多硫化物物种,而LiS则在最终放电过程中产生。微孔碳的狭窄孔隙可防止多硫化物溶解,并影响硫阴极的反应机理。