Details

Autor(en) / Beteiligte

• Li, Zhi
• Tan, Xuehai
• Li, Peng
• Kalisvaart, Peter
• Janish, Matthew T
• Mook, William M
• Luber, Erik J
• Jungjohann, Katherine L
• Carter, C. Barry
• Mitlin, David

Titel

Coupling In Situ TEM and Ex Situ Analysis to Understand Heterogeneous Sodiation of Antimony

Ist Teil von

• Nano letters, 2015-10, Vol.15 (10), p.6339-6348

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2015

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• We employed an in situ electrochemical cell in the transmission electron microscope (TEM) together with ex situ time-of-flight, secondary-ion mass spectrometry (TOF-SIMS) depth profiling, and FIB–helium ion scanning microscope (HIM) imaging to detail the structural and compositional changes associated with Na/Na+ charging/discharging of 50 and 100 nm thin films of Sb. TOF-SIMS on a partially sodiated 100 nm Sb film gives a Na signal that progressively decreases toward the current collector, indicating that sodiation does not proceed uniformly. This heterogeneity will lead to local volumetric expansion gradients that would in turn serve as a major source of intrinsic stress in the microstructure. In situ TEM shows time-dependent buckling and localized separation of the sodiated films from their TiN-Ge nanowire support, which is a mechanism of stress-relaxation. Localized horizontal fracture does not occur directly at the interface, but rather at a short distance away within the bulk of the Sb. HIM images of FIB cross sections taken from sodiated half-cells, electrically disconnected, and aged at room temperature, demonstrate nonuniform film swelling and the onset of analogous through-bulk separation. TOF-SIMS highlights time-dependent segregation of Na within the structure, both to the film-current collector interface and to the film surface where a solid electrolyte interphase (SEI) exists, agreeing with the electrochemical impedance results that show time-dependent increase of the films’ charge transfer resistance. We propose that Na segregation serves as a secondary source of stress relief, which occurs over somewhat longer time scales.