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Abstract Understanding of phase‐stability and nanoscale structural modulation during lithiation of layer materials demand comprehensive analysis of the Li‐containing phases in the solid‐state reaction products. Conventional chemical analysis methods in the transmission electron microscope (TEM) are not ideal to detect Li in partially intercalated nanodomains because Li atoms do not remain stationary under the focused electron beam. An alternate approach combining density functional theory (DFT) modeling and multislice image simulation has been explored in the present study to analyze the intercalated structures and to detect and quantify Li from the recorded high‐resolution TEM (HRTEM) micrographs of partially intercalated phases. HRTEM micrographs from partially lithiated graphite and MoS2show variations in the interlayer spacings, but are not usually directly interpretable. Hypothetical intercalated microstructures of graphite and MoS2supercells have been generated using atomic‐scale simulations with systematically varying Li concentrations. The measured interplanar spacings are compared with those of experimentally recorded HRTEM micrographs from lithiated graphite and MoS2. The results confirm the coexistence of different lithiated phases at localized domains. This understanding of phase transformation and the lithium quantification provides a basis for understanding the structural accommodation of layered materials during intercalation.
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Phase evolution and structural modulation during in situ lithiation of MoS2, WS2 and graphite in TEM
Abstract Li-ion batteries function by Li intercalating into and through the layered electrode materials. Intercalation is a solid-state interaction resulting in the formation of new phases. The new observations presented here reveal that at the nanoscale the intercalation mechanism is fundamentally different from the existing models and is actually driven by nonuniform phase distributions rather than the localized Li concentration: the lithiation process is a ‘distribution-dependent’ phenomena. Direct structure imaging of 2H and 1T dual-phase microstructures in lithiated MoS2and WS2along with the localized chemical segregation has been demonstrated in the current study. Li, a perennial challenge for the TEM, is detected and imaged using a low-dose, direct-electron detection camera on an aberration-corrected TEM and confirmed by image simulation. This study shows the presence of fully lithiated nanoscale domains of 2D host matrix in the vicinity of Li-lean regions. This confirms the nanoscale phase formation followed by Oswald ripening, where the less-stable smaller domains dissolves at the expense of the larger and more stable phases.
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- Award ID(s):
- 1820565
- PAR ID:
- 10223913
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Scientific Reports
- Volume:
- 11
- Issue:
- 1
- ISSN:
- 2045-2322
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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