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Development of the ReaxFF Reactive Force Field for Li/Mn/O Battery Technology with Application to Design a Self-Healing Cathode Electrolyte Interphase

Scope

ReaxFF for Li/Mn/O battery chemistry is developed and applied to cathode–electrolyte interphase (CEI) formation on LiMn₂O₄, focusing on a self-healing design with an ionic liquid–derived additive (PYR₁₃⁺).

Summary

The work targets lithium manganese oxide (LMO, LiMn₂O₄) cathodes, especially in high-reliability contexts such as implantable devices, where capacity fade and interfacial chemistry (SEI/CEI) affect safety. The authors motivate CEI (cathode electrolyte interphase) formation as less understood than SEI at the anode, and propose attaching an ion pair to the cathode surface to promote a self-healing CEI that seals cracks: bound cations limit cathode–electrolyte attack, while anions migrate to damaged regions and decompose preferentially relative to bulk electrolyte, reducing electrolyte loss and active-material loss. ReaxFF molecular dynamics, trained to ab initio reaction energies and barriers, is used to study CEI formation under experimentally inspired electrolyte compositions without fully ab initio cost.

Methods

  • ReaxFF training: The abstract states ReaxFF is trained against ab initio reaction energies and barriers for Li/Mn/O chemistry relevant to LiMn₂O₄ cathodes and CEI products; full QM program, functional, and training-set tables are in the article and Supporting Information (not in the short normalized/extracts/2024talkhoncheh-venue-manuscript_p1-2.txt front matter).
  • ReaxFF MD (CEI): Simulations target CEI formation on LMO with electrolyte chemistry involving PYR₁₃⁺ cations and FSI⁻ anions (abstract). System size, surface termination, electrolyte composition, ensemble, timestep, thermostat, and run length are not stated in the checked-in extract—read pdf_path (or version-of-record) for the computational protocol.

1 — MD application (ReaxFF on LiMn₂O₄). Engine: ReaxFF LAMMPS-class molecular dynamics (as in Computational Methods). System, PBC, slab termination, and electrolyte composition: N/A in this page summary — the p1–2 extract is front matter; pull cell size, atom counts, NVT/NPT choice, fs timestep, K-scale isothermal T (e.g. ~300 K for room-temperature interface MD is typical—confirm the K-listed T in pdf_path), and ps/ns duration from pdf_path. Barostat / stress / E-field (external), replica methods: N/A in the abstract-level summary on this page unless the full text adds them.

2 — Force-field training. Abstract states ReaxFF is trained to ab initio reaction energies and barriers for Li/Mn/O chemistry; SI and §2+ carry DFT code, level, and training structures (N/A to duplicate here on the stub).

3 — Static QM — the ab initio set underpins ReaxFF; standalone DFT results sections are part of the same article (full PDF).

Findings

CEI and additive (abstract). Simulations in the abstract support stronger, more stable cathode-side interphases on LMO when PYR₁₃⁺ is an electrolyte additive, a higher Li⁺ transference in those electrolytes, and a role for FSI⁻ vs PYR₁₃⁺ interactions in the trend. This is framed as a kinetic/thermodynamic story about reaction at the LMO/electrolyte interface; mechanism-level atomistic detail (e.g. catalytic steps on specific facets) requires the Results in pdf_path.

Comparisons to literature and outlook. The introduction situates the work next to Mn dissolution/impedance and cathode-side decomposition; open questions about long cycling and full reaction networks remain larger than the reactive ReaxFF window can resolve in one manuscript—as typical in FF-based interface studies.

Corpus honesty — galley pdf_path; use VOR for final pagination.

Limitations

The local corpus PDF is a galley (…_galley.pdf). CEI chemistry is complex; ReaxFF models require validation against experiment and QM for each new composition. Simulation time scales remain short relative to battery aging.

Relevance to group

Adri C. T. van Duin is corresponding author; the paper extends the group’s ReaxFF work into Li-ion cathode interfaces and medical-device battery narratives.

Citations and evidence anchors

Reader notes (navigation)

Use the full PDF at pdf_path for Computational methods tables not present in the short extract. Theme retrieval: paper-index-by-domain.