Transport Properties of Solid Electrolytes: Effect of the Isotope Composition of Lithium Charge Carriers

Bogomolov, M. Yu.; Pantyukhina, M. I.; Surin, A. A.; Obrosov, V. P.; Баталов, Н. Н.; Stepanov, A. P.; Суриков, В. Т.

doi:10.1023/b:ruel.0000046487.55515.a9

Cited by 3 publications

(5 citation statements)

References 4 publications

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“…In addition, all of the explored ternary chlorides have a room-temperature conductivity of >10 –4 S/cm, a promising trend for the family of our new compounds. The only candidate presented for LLXO systems, Li 5 SiN 3 , has previously been investigated as both a cathode and solid-electrolyte material. , This is exciting as the material is synthesizable and able to be assembled into a test cell.…”

Section: Discussionmentioning

confidence: 99%

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Electrolyte Coatings for High Adhesion Interfaces in Solid-State Batteries from First Principles

Ransom,

Ramdas,

Lomeli

et al. 2023

ACS Appl. Mater. Interfaces

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We introduce an adhesion parameter that enables rapid screening for materials interfaces with high adhesion. This parameter is obtained by density functional theory calculations of individual single-material slabs rather than slabs consisting of combinations of two materials, eliminating the need to calculate all configurations of a prohibitively vast space of possible interface configurations. Cleavage energy calculations are used as an upper bound for electrolyte and coating energies and implemented in an adapted contact angle equation to derive the adhesion parameter. In addition to good adhesion, we impose further constraints in electrochemical stability window, abundance, bulk reactivity, and stability to screen for coating materials for next-generation solid-state batteries. Good adhesion is critical in combating delamination and resistance to lithium diffusivity in solid-state batteries. Here, we identify several promising coating candidates for the Li7La3Zr2O12 and sulfide electrolyte systems including the previously investigated electrode coating materials LiAlSiO4 and Li5AlO8, making them especially attractive for experimental optimization and commercialization.

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Section: Discussionmentioning

confidence: 99%

“…The only candidate presented for LLXO systems, Li 5 SiN 3 , has previously been investigated as both a cathode and solid-electrolyte material. 51 , 52 This is exciting as the material is synthesizable and able to be assembled into a test cell.…”

Section: Discussionmentioning

confidence: 99%

Electrolyte Coatings for High Adhesion Interfaces in Solid-State Batteries from First Principles

Ransom,

Ramdas,

Lomeli

et al. 2023

ACS Appl. Mater. Interfaces

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“…Several studies have investigated the effects of isotopic substitution on the magnitude of ionic transport in Li + conducting borate glasses, [37][38][39][40] but, in general, there are not many studies of isotope effects in solid-state Li + battery materials. [41][42][43] In the study of reaction kinetics, it is commonly the ratio of the reaction rate constants that is used to quantify the isotope effect. 31,44 In that case, constant factors cancel out by taking the ratio.…”

Section: Spin Alignment Echo (Sae) This Measurement Technique Assesse...mentioning

confidence: 99%

Relating critical phonon occupation to activation barrier in fast lithium-ion conductors

Agne

Frerichs

Wang

et al. 2022

Preprint

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Phonon-based (vibrational) theories of ion transport are likely key to developing new design strategies for solid-state ionic conductors. However, they are not often utilized because it is difficult to ascertain which vibrational frequencies are important, even in describing fundamental parameters such as the activation barrier. This is perpetuated by the fact that it is difficult to tune vibrational frequencies directly, without changing the chemical structure, in order to study underlying phonon relations. Using isotopic substitution of 6Li for 7Li, we are able to change the mobile ion vibrations in the two exemplary ion conductors Li10SnP2S12 and Li6PS5Cl without altering their structure. Using a combination of nuclear magnetic resonance spectroscopy and ab initio molecular dynamics simulations to characterize temperature-dependent ion transport, it is demonstrated that the isotopic substitution of 6Li for 7Li increases the activation barrier for Li-ion transport. The magnitude of this isotope effect cannot be explained by changes in the zero-point vibrational energy alone. Therefore, we propose that the observed change in the activation barrier is related to the differences in the average critical phonon occupation needed to overcome the activation barrier. Our hypothesis is supported by an analytical model, based on the physics of quantum harmonic oscillators, that gives good agreement with the experimental results. Thus, isotopic substitution provides unique insights into the vibrational perspective and frequency dependence of the activation barrier in fast Li-ion conductors.

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“…Such a complex unit cell is known to be beneficial for lowering the thermal conductivity of the materials. , The cubic phase with high symmetry, as stabilized by introducing the dilute element, leads to high band degeneracy and large Seebeck coefficient . The tuning effects of the dilute elements on both electrical and thermal properties render the DECs ideal materials for thermoelectric applications. Some DECs found in our search are Li- or Na-rich, e.g., Li 6 (Mo/W)N 4 , − Li 7 (Nb/Ta)N 4 , , Li 7 MnN 4 , − Li 7 PS 6 , Na 6 MnCl 8 , Na 6 CdCl 8 , and Na 6 PbO 4 , which have been studied as electrodes or solid-state electrolytes (SSEs) in secondary batteries. The SSEs with high ionic conductivity are currently under intensive study. − The incorporation of dilute elements in Li or Na binary compounds, such as their oxides, sulfides, and nitrides, can introduce Li or Na vacancies, which facilitate the ionic conduction.…”

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confidence: 99%

“…Some DECs found in our search are Li- or Na-rich, e.g., Li 6 (Mo/W)N 4 , − Li 7 (Nb/Ta)N 4 , , Li 7 MnN 4 , − Li 7 PS 6 , Na 6 MnCl 8 , Na 6 CdCl 8 , and Na 6 PbO 4 , which have been studied as electrodes or solid-state electrolytes (SSEs) in secondary batteries. The SSEs with high ionic conductivity are currently under intensive study. − The incorporation of dilute elements in Li or Na binary compounds, such as their oxides, sulfides, and nitrides, can introduce Li or Na vacancies, which facilitate the ionic conduction.…”

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confidence: 99%

Dilute Element Compounds: A Route to Enriching Inorganic Functional Materials

Lin

Chen

Sun

2021

J. Phys. Chem. Lett.

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Transport Properties of Solid Electrolytes: Effect of the Isotope Composition of Lithium Charge Carriers

Cited by 3 publications

References 4 publications

Electrolyte Coatings for High Adhesion Interfaces in Solid-State Batteries from First Principles

Electrolyte Coatings for High Adhesion Interfaces in Solid-State Batteries from First Principles

Relating critical phonon occupation to activation barrier in fast lithium-ion conductors

Dilute Element Compounds: A Route to Enriching Inorganic Functional Materials

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