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Superionic Solid Electrolyte Li₇La₃Zr₂O₁₂ Synthesis and Thermodynamics for Application in All-Solid-State Lithium-Ion Batteries.

ABSTRACT: Solid-state reaction was used for Li₇La₃Zr₂O₁₂ material synthesis from Li₂CO₃, La₂O₃ and ZrO₂ powders. Phase investigation of Li₇La₃Zr₂O₁₂ was carried out by x-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS) methods. The thermodynamic characteristics were investigated by calorimetry measurements. The molar heat capacity (C_p,m), the standard enthalpy of formation from binary compounds (Δ_oxH_LLZO) and from elements (Δ_fH_LLZO), entropy (S⁰₂₉₈), the Gibbs free energy of the Li₇La₃Zr₂O₁₂ formation (∆_f G⁰₂₉₈) and the Gibbs free energy of the LLZO reaction with metallic Li (∆_rG_LLZO/Li) were determined. The corresponding values are C_p,m = 518.135 + 0.599 × T - 8.339 × T^-2, (temperature range is 298-800 K), Δ_oxH_LLZO = -186.4 kJ·mol^-1, Δ_fH_LLZO = -9327.65 ± 7.9 kJ·mol^-1, S⁰₂₉₈ = 362.3 J·mol^-1·K^-1, ∆_f G⁰₂₉₈ = -9435.6 kJ·mol^-1, and ∆_rG_LLZO/Li = 8.2 kJ·mol^-1, respectively. Thermodynamic performance shows the possibility of Li₇La₃Zr₂O₁₂ usage in lithium-ion batteries.

SUBMITTER: Aleksandrov D

PROVIDER: S-EPMC8746261 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The formation of a solid electrolyte interphase (SEI) between the anode surface and the electrolyte of lithium-ion batteries (LIBs) has been considered to be the most important yet the least understood issue of LIBs. To further our understanding in this regard, the density functional theory (DFT) B3PW91/6-311++G(3df,3pd) together with the implicit solvent model and the transition state theory were used for the first time to comprehensively explore the electroreduction mechanism of a novel additive, 4-chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), and a few other solvents and additives, such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), fluoroethylene carbonate (FEC), and even ethylene sulfite (ES), for comparison. The one-electron reduction potential of Li+-coordinated compounds Li+(X) for forming decomposition precursors [c-Li+(X˙-)] decreases in the following sequence: CMDO (1.9-2.2 V vs. Li+/Li) ∼ ES(1.9 V) > FEC (0.7 V) > EC (0.47 V) > PC (0.45 V) > DMC (0.38 V); this implies that CMDO is reduced prior to other solvents or additives in the mixture. Although the ring opening of [c-Li+(CMDO˙-)] is the least kinetically favorable, as reflected by the highest energy barrier (E a), i.e., CMDO (18.8-22.9 kcal mol-1) ∼ ES (23.4) > FEC (16.2) > PC (12.5) > EC (11.2) > DMC (8.0), CMDO still shows the highest overall reaction rate constant (∼1053 s-1) for forming an open ring radical [o-Li+(CMDO˙)-]. In addition, the termination reaction of [o-Li+(CMDO˙)-] for forming LiCl is thermodynamically more favorable than that of Li2SO3 or organic disulfite (LiSO3)2-R, which supports the experimental observation that the halogen-containing LiF or LiCl additives are predominant over all other halogen-containing species in the SEI layer. Moreover, the hybrid model by including the second solvation shell of Li+ via a supercluster [(CMDO)Li+(PC)2](PC)9 and the implicit solvent model (SMD) can result in a reduction potential (∼1.7 V) that is in excellent agreement with the experimental reduction peak.

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Superionic Solid Electrolyte Li₇La₃Zr₂O₁₂ Synthesis and Thermodynamics for Application in All-Solid-State Lithium-Ion Batteries.

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Superionic Solid Electrolyte Li₇La₃Zr₂O₁₂ Synthesis and Thermodynamics for Application in All-Solid-State Lithium-Ion Batteries.