Operando Grazing Incidence Small-Angle X-ray Scattering/X-ray Diffraction of Model Ordered Mesoporous Lithium-Ion Battery Anodes.
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 NiCo2O4anode 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.
Sarang M
SM
Bhaway
Zhe
Z
Qiang
Yanfeng
Y
Xia
Xuhui
X
Xia
X-ray Science Division, Advanced Photon Source, Center for Nanoscale Materials, Argonne National Laboratory , Argonne, Illinois 60439, United States.
Byeongdu
0000-0003-2514-8805
B
Lee
Center for Functional Nanomaterials, Brookhaven National Laboratory , Upton, New York 11973, United States.
Kevin G
KG
Yager
Center for Functional Nanomaterials, Brookhaven National Laboratory , Upton, New York 11973, United States.
Lihua
L
Zhang
Center for Functional Nanomaterials, Brookhaven National Laboratory , Upton, New York 11973, United States.
Kim
K
Kisslinger
Yu-Ming
YM
Chen
Kewei
K
Liu
Yu
Y
Zhu
Bryan D
0000-0003-1916-7145
BD
Vogt
cooperative assembly; metal oxide anode; nanoporous