Year: 2026
Type: preprint
Abstract: Graphite's structural and electronic response to molecular intercalation is central to its performance as a carbon-based electrode material, yet the microscopic coupling between subsurface intercalation and surface adsorption remains poorly understood. We present a first-principles investigation of AlF3 adsorption and intercalation in graphite to explain the microscopic origin of a recently observed two-step self-limiting sorption mechanism. Using density functional theory (DFT-D3), we show that a single intercalated AlF3 molecule locally transforms the structure, electronic properties, and diffusion behavior of graphite through a blister-like surface deformation. Comparing pristine graphite with a graphite surface containing a subsurface intercalated molecule, coverage-dependent adsorption energetics reveal a crossover from repulsive lateral interactions to cooperative binding above the blister, driven by local curvature and intercalation-induced charge redistribution. Diffusion-barrier calculations show that the blister simultaneously acts as a kinetic trap, raising diffusion barriers and transitioning surface mobility from a quasi-barrierless to a thermally activated regime. Charge-density difference and Mulliken population analyses identify the intercalant as a stable electronic reservoir that deepens the surface potential landscape, kinetically immobilizing adsorbed species. Together, these results establish a structure-property relationship for intercalation-induced deformation in graphite, offering a quantitative framework for controlling intercalation efficiency in carbon-based energy storage and conversion systems.
Source: arXiv (Cornell University)
Institutions: Instituto de Física del Litoral, Bariloche Atomic Centre
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: green
Funders: European Commission, Ministerstvo Školství, Mládeže a Tělovýchovy, Consejo Nacional de Investigaciones Científicas y Técnicas, Universidad Nacional del Litoral, Universidad de Zaragoza, Agencia Santafesina de Ciencia, Tecnología e Innovación, Horizon 2020 Framework Programme, Agencia Nacional de Promoción Científica y Tecnológica
Awards: G1711002585, G1804852580, G2198898644, G228132043, G2358120131, G2744761368, G2779949270, G2882798528, G2998108568, G3034095715, G3337907308, G3345895242, G3399339667, G3477743816, G3771185154, G4273056302, G4655014523, G535059049, Energy Waste Recovery and Gas Treatment, G574631162, G6402224719, G6666489062, G6880138866, G7087439764, ULtra ThIn MAgneto Thermal sEnsor-Ing, G8044956214, G8512683158, G8732257632, G9644609, G981663960
OpenAlex ID: W7201848900
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