Solid electrolyte interphase formation between the Li0.29La0.57TiO3solid-state electrolyte and a Li-metal anode: anab initiomolecular dynamics study

Galvez-Aranda, Diego E.; Seminario, Jorge M.

doi:10.1039/c9ra10984f

Cited by 12 publications

(9 citation statements)

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“…Such elucidation would require much longer times of simulation and larger unit cells for better statistics; actually, it would require a totally different strategy. Therefore, the use of MSDs in our simulations is to determine the solvation of the ions but not to determine their diffusion coefficients. , This is a transient-state study and diffusion analysis would require a steady-state study; therefore, the mean-squared displacements shown in Figure cannot be used to determine any related property such as diffusion mechanisms and constants.…”

Section: Results and Discussionmentioning

confidence: 99%

“…There are recent developments in the study of interfaces at batteries using directly external electric fields; some of them are presented here. Galvez-Aranda and Seminario 27 studied the Li 0.29 La 0.57 TiO 3 solid-state electrolyte in a nanobattery using ab initio molecular dynamics simulations, finding that the SSE decomposes in contact with the Li-metal, forming lithium oxide at the interface, even without the effect of the external field. Once the external field was applied with intensities from 0.5 to 2 V/Å, they found that the electric field accelerated the formation of lithium oxide at the interface.…”

Section: Introductionmentioning

confidence: 99%

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Li-Metal Anode in Dilute Electrolyte LiFSI/TMP: Electrochemical Stability Using Ab Initio Molecular Dynamics

Galvez-Aranda

Seminario

2020

J. Phys. Chem. C

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Ab initio molecular dynamics simulations were performed for Li+-conducting electrolytes based on trimethyl phosphates (TMP) and lithium bis(fluorosulfonyl)imide (Li+FSI–) salt in contact with a Li-metal electrode. We focused on the transient-state behavior at the electrolyte, interfacial electrolyte–Li-metal electrode, and lithium reference electrode–electrolyte–Li-metal electrode to study dynamics and activation energy barriers of the Li+ ion, electrochemical and thermal stability of the interface electrode–electrolyte, and potential behavior of the Li-metal electrode, respectively. Our results show that in the most stable state, Li+ ions are tetrahedrally coordinated to three TMP and one FSI–. The inner solvation shell of a Li ion is composed of three TMP and one FSI– in one contact ion pair and four TMP in a solvent-separated ion pair. On the other hand, Li ions transporting through electrolyte cages take place when they are coordinated with three or less molecules that could be a combination of TMP and FSI–. The decomposition pathway of the LiFSI salt when in direct contact with the Li-metal anode starts with defluorination of FSI–, rapidly losing F– to the lithium surface, forming LiF species. The remaining FSO2NSO2 –2 with the addition of 2e– from the Li-metal decomposes into SO2 –2 and NFSO2 –2. SO2 –2 deposits on the Li surface and decomposes into Li2O and Li2S. The remaining NFSO2 –2 defluorinates, losing F– ion to the lithium surface, resulting in LiF and the remaining NSO2 –1 deposits on the lithium surface and decomposes in the following picoseconds, forming several binary compounds such as Li3N, Li2S, and Li2O. In contrast, when the salt is solvated by the TMP molecules, avoiding a direct contact with the Li-metal electrode, only one defluorination occurs, decomposing the FSI– into FSO2NSO2 –2 and F–. The two anions remain stable as they are solvated by the TMP molecules. We also analyzed the open-circuit potential energy (OCPE) of the Li-metal electrode during the solid-electrolyte interphase (SEI) formation. OCPE is calculated from the average local potential profile difference within the Li-metal electrode and a pristine Li-crystal reference electrode (LRE). When no SEI is formed, the Li-metal electrode has an average OCPE of +0.36 eV vs LRE. Due to the formation of an SEI, the Li-metal electrode has an average OCPE between −0.07 and −0.21 eV vs LRE. The OCPE of the Li-metal electrode decreases by ∼0.42 eV when an SEI is formed.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Li-Metal Anode in Dilute Electrolyte LiFSI/TMP: Electrochemical Stability Using Ab Initio Molecular Dynamics

Galvez-Aranda

Seminario

2020

J. Phys. Chem. C

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“…As is known to all, the semicircle in the high frequency region is attributed to the interface resistance of the surface membrane on the electrode active particles, and the semicircle in the medium-to-low frequency region is ascribed to the charge transfer resistance between the electrode active particles and LE. [36][37][38] In Fig. 7a, the interfacial resistance of the pristine LCO is higher than that of the 3-PHL-LCO before cycles.…”

Section: Electrochemical Characterizationmentioning

confidence: 92%

Direct surface coating of high voltage LiCoO₂ cathode with P(VDF-HFP) based gel polymer electrolyte

Hui-ling¹,

Wen²,

Wang³

et al. 2020

RSC Adv.

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“…Liu et al [82] confirmed that black LLTO showed two new peaks at the lower binding energies corresponding to the formation of Ti 3+ with lower electron densities. Galvez-Aranda et al [83] identified that Ti reduction occurs at the LLTO/Li metal interface. The reaction rate at the interface increases as the applied external electric field increases corresponding to an electrochemical instability of the LLTO/Li-metal interface.…”

Section: Ti Reduction At the Interfacementioning

confidence: 99%

Perovskite Solid-State Electrolytes for Lithium Metal Batteries

et al. 2021

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Solid-state lithium metal batteries (LMBs) have become increasingly important in recent years due to their potential to offer higher energy density and enhanced safety compared to conventional liquid electrolyte-based lithium-ion batteries (LIBs). However, they require highly functional solid-state electrolytes (SSEs) and, therefore, many inorganic materials such as oxides of perovskite La2/3−xLi3xTiO3 (LLTO) and garnets La3Li7Zr2O12 (LLZO), sulfides Li10GeP2S12 (LGPS), and phosphates Li1+xAlxTi2−x(PO4)3x (LATP) are under investigation. Among these oxide materials, LLTO exhibits superior safety, wider electrochemical window (8 V vs. Li/Li+), and higher bulk conductivity values reaching in excess of 10−3 S cm−1 at ambient temperature, which is close to organic liquid-state electrolytes presently used in LIBs. However, recent studies focus primarily on composite or hybrid electrolytes that mix LLTO with organic polymeric materials. There are scarce studies of pure (100%) LLTO electrolytes in solid-state LMBs and there is a need to shed more light on this type of electrolyte and its potential for LMBs. Therefore, in our review, we first elaborated on the structure/property relationship between compositions of perovskites and their ionic conductivities. We then summarized current issues and some successful attempts for the fabrication of pure LLTO electrolytes. Their electrochemical and battery performances were also presented. We focused on tape casting as an effective method to prepare pure LLTO thin films that are compatible and can be easily integrated into existing roll-to-roll battery manufacturing processes. This review intends to shed some light on the design and manufacturing of LLTO for all-ceramic electrolytes towards safer and higher power density solid-state LMBs.

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Solid electrolyte interphase formation between the Li_0.29La_0.57TiO₃solid-state electrolyte and a Li-metal anode: anab initiomolecular dynamics study

Abstract: An ab initio molecular dynamics study of an electrochemical interface between a solid-state-electrolyte Li0.29La0.57TiO3 and Li-metal to analyze interphase formation and evolution when external electric fields are applied.

Cited by 12 publications

References 48 publications

Li-Metal Anode in Dilute Electrolyte LiFSI/TMP: Electrochemical Stability Using Ab Initio Molecular Dynamics

Li-Metal Anode in Dilute Electrolyte LiFSI/TMP: Electrochemical Stability Using Ab Initio Molecular Dynamics

Direct surface coating of high voltage LiCoO₂ cathode with P(VDF-HFP) based gel polymer electrolyte

Perovskite Solid-State Electrolytes for Lithium Metal Batteries

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Solid electrolyte interphase formation between the Li0.29La0.57TiO3solid-state electrolyte and a Li-metal anode: anab initiomolecular dynamics study

Abstract: An ab initio molecular dynamics study of an electrochemical interface between a solid-state-electrolyte Li0.29La0.57TiO3 and Li-metal to analyze interphase formation and evolution when external electric fields are applied.

Cited by 12 publications

References 48 publications

Li-Metal Anode in Dilute Electrolyte LiFSI/TMP: Electrochemical Stability Using Ab Initio Molecular Dynamics

Li-Metal Anode in Dilute Electrolyte LiFSI/TMP: Electrochemical Stability Using Ab Initio Molecular Dynamics

Direct surface coating of high voltage LiCoO2 cathode with P(VDF-HFP) based gel polymer electrolyte

Perovskite Solid-State Electrolytes for Lithium Metal Batteries

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Product

Resources

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Solid electrolyte interphase formation between the Li_0.29La_0.57TiO₃solid-state electrolyte and a Li-metal anode: anab initiomolecular dynamics study

Direct surface coating of high voltage LiCoO₂ cathode with P(VDF-HFP) based gel polymer electrolyte