Wang Xinyue, Wang Si-Cong, Ma Junjie, Xie Ruo-Chen, Wang Wei
State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, ChemBIC (Chemistry and Biomedicine Innovation Center), Nanjing University Nanjing 210023 China
Chem Sci. 2024 May 10;15(22):8536-8544. doi: 10.1039/d4sc00072b. eCollection 2024 Jun 5.
While optical microscopy of single particle electrochemistry has proven insightful for future nanoparticle-based batteries, little is explored for micron-sized particles of more practical interest. This is largely hindered by the currently limited methodology. Accordingly, we report transmission optical microscopy using near-infrared light for accessing intra-particle electrochemistry in virtue of strong light penetration as compared to visible light. Using near-infrared ( > 730 nm) bright-field microscopy, the redox electrochemistry of single LiCoO microparticles can be readily measured based on the measurements of optical contrast changes during electrochemical cycling. Further using the established methodology, we discover that the solid-state diffusion inside most single microparticles is distinctly directional, instead of in an isotropic manner from outer to inner as observed for the other particles. This phenomenon is also observed using dark field scattering microscopy with near-infrared light, suggesting non-uniform crystal inner structures responsible for the geometrically asymmetric heterogeneity of charge transfer kinetics within each single particle. These results indicate potential opportunities offered by the near-infrared optical methodology for studying practical battery materials.
虽然单粒子电化学的光学显微镜已被证明对未来基于纳米粒子的电池具有重要意义,但对于更具实际应用价值的微米级粒子的研究却很少。这在很大程度上受到当前有限方法的阻碍。因此,我们报告了一种使用近红外光的透射光学显微镜,与可见光相比,由于光穿透性强,该显微镜可用于研究粒子内部的电化学。使用近红外(>730 nm)明场显微镜,基于电化学循环过程中光学对比度变化的测量,可以很容易地测量单个LiCoO微粒的氧化还原电化学。进一步使用已建立的方法,我们发现大多数单个微粒内部的固态扩散具有明显的方向性,而不是像其他粒子那样从外到内呈各向同性。使用近红外光的暗场散射显微镜也观察到了这种现象,这表明晶体内部结构不均匀,导致每个单个粒子内电荷转移动力学的几何不对称异质性。这些结果表明近红外光学方法在研究实际电池材料方面具有潜在的机会。