Predictive stochastic analysis of massive filter-based electrochemical reaction networks

Chemical reaction networks (CRNs) are powerful tools for obtaining mechanistic insight into complex reactive processes. However, they are limited in their applicability where reaction mechanisms are not well understood and products are unknown. Here we report new methods of CRN generation and analysis that overcome these limitations. By constructing CRNs using filters rather than templates, we can capture species and reactions that are unintuitive but fundamentally reasonable. The resulting massive CRNs can then be interrogated via stochastic methods, revealing thermodynamically bounded reaction pathways to species of interest and automatically identifying network products. We apply this methodology to study solid-electrolyte interphase (SEI) formation in Li-ion batteries, generating a CRN with ~86,000,000 reactions. Our methods automatically recover SEI products from the literature and predict previously unknown species. We validate their formation mechanisms using first-principles calculations, discovering novel kinetically accessible molecules. This methodology enables the de novo exploration of vast chemical spaces, with the potential for diverse applications across thermochemistry, electrochemistry, and photochemistry.

Safe and Stable Lithium Metal Batteries Enabled by an Amide-Based Electrolyte

Highlights A novel amide-based nonflammable electrolyte is proposed. The formation mechanism and solvation chemistry are investigated by molecular dynamics simulations and density functional theory. An inorganic/organic-rich solid electrolyte interphase with an abundance of LiF, Li3N and Li–N–C is in situ formed, leading to spherical lithium deposition. The amide-based electrolyte can enable stable cycling performance at room temperature and 60 ℃. Abstract The formation of lithium dendrites and the safety hazards arising from flammable liquid electrolytes have seriously hindered the development of high-energy-density lithium metal batteries. Herein, an emerging amide-based electrolyte is proposed, containing LiTFSI and butyrolactam in different molar ratios. 1,1,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropylether and fluoroethylene carbonate are introduced into the amide-based electrolyte as counter solvent and additives. The well-designed amide-based electrolyte possesses nonflammability, high ionic conductivity, high thermal stability and electrochemical stability (> 4.7 V). Besides, an inorganic/organic-rich solid electrolyte interphase with an abundance of LiF, Li3N and Li–N–C is in situ formed, leading to spherical lithium deposition. The formation mechanism and solvation chemistry of amide-based electrolyte are further investigated by molecular dynamics simulations and density functional theory. When applied in Li metal batteries with LiFePO4 and LiMn2O4 cathode, the amide-based electrolyte can enable stable cycling performance at room temperature and 60 ℃. This study provides a new insight into the development of amide-based electrolytes for lithium metal batteries.

Effect of the supergravity on the formation and cycle life of non-aqueous lithium metal batteries

Extra-terrestrial explorations require electrochemical energy storage devices able to operate in gravity conditions different from those of planet earth. In this context, lithium (Li)-based batteries have not been fully investigated, especially cell formation and cycling performances under supergravity (i.e., gravity > 9.8 m s−2) conditions. To shed some light on these aspects, here, we investigate the behavior of non-aqueous Li metal cells under supergravity conditions. The physicochemical and electrochemical characterizations reveal that, distinctly from earth gravity conditions, smooth and dense Li metal depositions are obtained under supergravity during Li metal deposition on a Cu substrate. Moreover, supergravity allows the formation of an inorganic-rich solid electrolyte interphase (SEI) due to the strong interactions between Li+ and salt anions, which promote significant decomposition of the anions on the negative electrode surface. Tests in full Li metal pouch cell configuration (using LiNi0.8Co0.1Mn0.1O2-based positive electrode and LiFSI-based electrolyte solution) also demonstrate the favorable effect of the supergravity in terms of deposition morphology and SEI composition and ability to carry out 200 cycles at 2 C (400 mA g−1) rate with a capacity retention of 96%.