Operando Grazing Incidence Small-Angle X-ray Scattering/X-ray Diffraction of Model Ordered Mesoporous Lithium-Ion Battery Anodes
Citation
Bhaway, S.M; Qiang, Z.; Xia, Y.; Xia, X.; Lee, B.; Yager, K.G.; Zhang, L.; Kisslinger, K.; Chen, Y.-M.; Liu, K.; Zhu, Y.; Vogt, B.D. "Operando Grazing Incidence Small-Angle X-ray Scattering/X-ray Diffraction of Model Ordered Mesoporous Lithium-Ion Battery Anodes"
ACS Nano 2017,
11 1443–1454.
doi: 10.1021/acsnano.6b06708Summary
GISAXS/GIXD measurements during operation of a model lithium-ion battery anode are used to understand how mesoporous materials can impact battery performance.
Abstract
Emergent lithium-ion (Li+) batteries commonly rely on nanostructuring of the active electrode materials to decrease the Li+ ion diffusion path length and to accommodate the strains associated with the insertion and de-insertion of Li+, but in many cases these nanostructures evolve during electrochemical charging–discharging. This change in the nanostructure can adversely impact performance, and challenges remain regarding how to control these changes from the perspective of morphological design. In order to address these questions, operando grazing-incidence small-angle X-ray scattering and X-ray diffraction (GISAXS/GIXD) were used to assess the structural evolution of a family of model ordered mesoporous NiCo2O4 anode films during battery operation. The pore dimensions were systematically varied and appear to impact the stability of the ordered nanostructure during the cycling. For the anodes with small mesopores (?9 nm), the ordered nanostructure collapses during the first two charge–discharge cycles, as determined from GISAXS. This collapse is accompanied by irreversible Li-ion insertion within the oxide framework, determined from GIXD and irreversible capacity loss. Conversely, anodes with larger ordered mesopores (17–28 nm) mostly maintained their nanostructure through the first two cycles with reversible Li-ion insertion. During the second cycle, there was a small additional deformation of the mesostructure. This preservation of the ordered structure lead to significant improvement in capacity retention during these first two cycles; however, a gradual loss in the ordered nanostructure from continuing deformation of the ordered structure during additional charge–discharge cycles leads to capacity decay in battery performance. These multiscale operando measurements provide insight into how changes at the atomic scale (lithium insertion and de-insertion) are translated to the nanostructure during battery operation. Moreover, small changes in the nanostructure can build up to significant morphological transformations that adversely impact battery performance through multiple charge–discharge cycles.
