Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries

Abstract

Dendrite free electrodeposition of lithium metal is necessary for the adoption of high energy density rechargeable lithium metal batteries. Here, we demonstrate a new mechanism of using a liquid crystalline electrolyte to suppress dendrite growth with a lithium metal anode. A nematic liquid crystalline electrolyte modifies the kinetics of electrodeposition by introducing additional overpotential due to its bulk distortion and anchoring free energy. By extending the phase-field model, we simulate the morphological evolution of the metal anode and explore the role of bulk distortion and anchoring strengths on the electrodeposition process. We find that adsorption energy of liquid crystalline molecules on lithium surface can be a good descriptor for the anchoring energy and obtain it using first-principles density functional theory calculations. Unlike other extrinsic mechanisms, we find that liquid crystals with high anchoring strengths can ensure smooth electrodeposition of lithium metal, thus paving the way for practical applications in rechargeable batteries based on metal anodes.

arXiv comment28 pages, 5 figures, 1 table, 18 pages of Supporting Information. v2: added molecular level calculations and design rules

References in corpus (14)

• A real-space grid implementation of the Projector Augmented Wave method
• Stable Lithium Electrodeposition in Liquid and Nanoporous Solid Electrolytes
• Phase-Field Formulation for Quantitative Modeling of Alloy Solidification
• Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics
• Understanding shape entropy through local dense packing
• Unified derivation of phase-field models for alloy solidification from a grand-potential functional
• Machine Learning Enabled Computational Screening of Inorganic Solid Electrolytes for Dendrite Suppression with Li Metal Anode
• Phase-field simulations of lithium dendrite growth with open-source software
• Stability of Electrodeposition at Solid-Solid Interfaces and Implications for Metal Anodes
• Universal Chemomechanical Design Rules for Solid-Ion Conductors to Prevent Dendrite Formation in Lithium Metal Batteries
• Rapid multiphase-field model development using a modular free energy based approach with automatic differentiation in MOOSE/MARMOT
• Mathematics and liquid crystals
• Descriptors for Electrolyte-Renormalized Oxidative Stability of Solvents in Lithium-ion Batteries
• Role of anisotropy in determining stability of electrodeposition at solid-solid interfaces

Cited by in corpus (4)

• Interfacial Effects on Solid Electrolyte Interphase in Lithium-ion Batteries
• Constriction and contact impedance of ceramic solid electrolytes
• Chemomechanics: friend or foe of the "AND problem" of solid-state batteries?
• Modelling structure and ionic diffusion in a class of ionic liquid crystal-based solid electrolytes