Identification of Solid-Electrolyte Interphase Species by Joint Characterization of Li-ion Battery Chemistry by Mass Spectrometry and Electro-Chemical Reaction Networks

TL;DR

This study combines computational modeling and mass spectrometry to identify and understand the complex molecular composition and formation pathways of the solid electrolyte interphase in lithium-ion batteries, significantly expanding current knowledge.

Contribution

It introduces a comprehensive computational-experimental framework that uncovers new SEI species and reaction mechanisms without relying on predefined assumptions.

Findings

Predicted 28 novel SEI species, nearly doubling known species.

Constructed the largest eCRN with over 10,000 species and 209 million reactions.

Confirmed new species through advanced mass spectrometry analysis.

Abstract

The formation and stability of the solid electrolyte interphase (SEI) play a central role in determining the long-term performance and safety of modern electrochemical energy storage systems. Despite decades of research, the SEI's heterogeneous, dynamic, and multi-phase nature has defied comprehensive molecular-level characterization, creating a critical knowledge gap that limits rational battery design. In this work, we introduce a computational-experimental framework that integrates high-throughput quantum chemistry calculations, data-driven electro-chemical reaction networks (eCRNs), stochastic algorithms, and Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (LDI-FTICR-MS) to unravel SEI formation in carbonate-based electrolytes without imposing predefined mechanisms. We constructed the most comprehensive eCRN to date, spanning over 10,000 species and 209 million reactions. Through stochastic network analysis, we successfully recovered 27 species that were previously reported in literature and predicted 28 novel SEI species, nearly doubling our scientific knowledge in this area. Each new species was rigorously confirmed through advanced mass spectra analysis of its distinct molecular and isotopic signatures. We kinetically refined the formation pathways for a select set of both previously reported and novel SEI products, revealing kinetically feasible elementary reaction mechanisms with activation barriers below 1 eV. This computational-experimental approach deepens our molecular-level understanding of SEI chemistry and supports the rational design of advanced electrolytes and engineered interphases for next-generation lithium-based batteries.