Computational Study of Li Ion Electrolytes Composed of Li3AsS4Alloyed with Li4GeS4

Al-Qawasmeh, Ahmad; Holzwarth, N. A. W.

doi:10.1149/2.1131609jes

Cited by 11 publications

(20 citation statements)

References 42 publications

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“…The partial density of states of Li 4 GeS 0 4 in its ground state structure was previously presented in Ref. 27. While, density functional theory is known to systematically underestimate the band gaps, the relative band gaps are usually well represented.…”

Section: Electronic Structure Resultsmentioning

confidence: 99%

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Al-Qawasmeh

Howard

Holzwarth

2017

J. Electrochem. Soc.

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Recent experimental literature reports the solid state electrolyte properties of Li 4 SnS 4 and Li 4 SnSe 4 , identifying interesting questions regarding their structural details and motivating our first principles simulations. Together with Li 4 GeS 4 , these materials are all characterized by the orthorhombic space group Pnma and are found to be isostructural. They have a ground state crystal structure (denoted Li 4 SnS 0 4 ) having interstitial sites in void channels along the c-axis. They also have a meta-stable structure (denoted Li 4 SnS * 4 ) which is formed by moving one fourth of the Li ions from their central sites to the interstitial positions, resulting in a 0.5 Å contraction of the a lattice parameter. Relative to their ground states, the meta-stable structures are found to have energies 0.25 eV, 0.02 eV, and 0.07 eV for Li 4 From this literature, some interesting questions arise regarding crystal structures and mechanisms for ion mobility. In order to address these questions, we use first principles methods to examine the ideal crystal forms and defect structures of Li 4 SnS 4 and the structurally and chemically related materials Li 4 GeS 4 and Li 4 SnSe 4 . For each of these materials, we identify two closely related structures -an ideal ground state structure and an ideal meta-stable structure. The simulations show that the meta-stable structural form is most accessible to Li 4 SnS 4 of the three materials studied. The simulations are extended to study mechanisms of Li ion migration in both Li 4 SnS 4 and Li 4 SnSe 4 and are related to the experimental results reported in the literature. Computational MethodsThe computational methods used in this work are based on density functional theory (DFT), 8,9 using the projected augmented wave (PAW) 10 formalism. The PAW basis and projector functions were generated by the ATOMPAW 11 code and the crystalline materials were modeled using the QUANTUM ESPRESSO 12 and ABINIT 13 packages. Visualizations were constructed using the XCrySDEN, 14 The exchange correlation function is approximated using the localdensity approximation (LDA). 17 The choice of LDA functional was made based on previous investigations 18-20 of similar materials which showed that, provided that the lattice constants are scaled by a correction factor of 1.02, the simulations are in good agreement with experiment, especially lattice vibrational frequencies and heats of formation. The partial densities of states were calculated as described in previous work, 20,21 using weighting factors based on the charge within the augmentation spheres of each atom with radii r The calculations were well converged with plane wave expansions of the wave function including |k + G| 2 ≤ 64 bohr −2 . Calculations for the conventional unit cells were performed using a Brillouin-zone sampling grid of 4 × 8 × 8. Simulations of Li ion migration were performed at constant volume in supercells constructed from the optimized conventional cells extended by 1 × 2 × 2 and a Brillouin-zone sampling grid of 2 × 2 × 2. In ...

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Section: Electronic Structure Resultsmentioning

confidence: 99%

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Al-Qawasmeh

Howard

Holzwarth

2017

J. Electrochem. Soc.

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“…AIMD simulation studies of other Li sulfide SEs, such as Li 7 P 3 S 11 and argyrodite Li 6 PS 5 Cl, confirmed their exceptionally fast Li‐ion diffusion in bulk phases. In addition to these AIMD simulation studies, which quantified the overall diffusional properties, static first principles studies including NEB calculations have also been performed on Li sulfide SEs, such as Li 3 PS 4 , Li 4 GeS 4 , Li 4 SnS 4 , and Li 3 AsS 4 , to investigate the formation energies of mobile Li + vacancies and interstitials, Li + site energies in the structures, and Li + migration energy barriers …”

Section: Li‐ion Transport In Li‐ion Sesmentioning

confidence: 99%

Design Strategies, Practical Considerations, and New Solution Processes of Sulfide Solid Electrolytes for All‐Solid‐State Batteries

Park

Bai

Kim

et al. 2018

Advanced Energy Materials

473

274

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Since the first demonstration of prototype Li batteries (TiS 2 /Li) in 1976, [1] the develo pment of LIBs to date has been strongly affected by safety issues. One of the major technical breakthroughs for the commer cialization of LIBs was the replacement of Li metal with carbonaceous materials as the anode. [2][3][4] It is well known that the use of Li metal was challenged by serious safety concerns associated with internal short circuit by the dendritic growth of Li metal. [5][6][7] The everrising requirements for higher energy density of LIBs have raised more serious safety concerns. Raising the upper cutoff voltages leads to poorer sta bility at electrode-electrolyte interfaces. [8,9] Ultrathinning the polymeric separators to less than 10 µm, despite the reinforce ments using ceramic materials, [10][11][12] result in more vulnerability toward internal short circuits. These may also be related to degassing, fire, and explosion accidents of LIBs in recent years. Further more, largescale applications of LIBs, such as batterydriven electric vehicles and gridscale energy storages, face unprecedented challenges in terms of safety requirements. [13][14][15] In this regard, solidification of conventional flammable organic liquid electrolytes with inorganic materials, such as superionic conductor solid electrolytes (SEs), is an ideal solution. [16][17][18][19][20][21][22][23][24][25] Another strong motivation in the development of SEs is to unleash the harness of limited energy density for con ventional LIBs by using SEs to stabilize and enable alternative highcapacity electrode materials, such as Li metal anode and sulfur cathode. [15,23] Additionally, the design of allsolidstate Li or Liion batteries (ALSBs) by stacking bipolar electrodes allows the minimization of inactive encasing materials, thereby increasing celllevel energy density. [22,26] The first superionic conductors PbF 2 and Ag 2 S were discov ered by Michael Faraday in 1838. [27] Since then, several notable progresses in the field of solidstate superionic conductors and their newly enabled electrochemical devices had occurred; [27] the development of oxygenion conductors (Ydoped ZrO 2 ) applied to solid oxide fuel cells, the discoveries of Ag + superionic conduc tors (e.g., RbAg 4 I 5 ), and the development of Naion conducting sodium beta alumina (β″Al 2 O 3 ). Currently, it is a promi sing opportunity for Liion SEs to revolutionize LIB technologies Owing to the ever-increasing safety concerns about conventional lithium-ion batteries, whose applications have expanded to include electric vehicles and grid-scale energy storage, batteries with solidified electrolytes that utilize nonflammable inorganic materials are attracting considerable attention. In particular, owing to their superionic conductivities (as high as ≈10 −2 S cm −1 ) and deformability, sulfide materials as the solid electrolytes (SEs) are considered the enabling material for high-energy bulk-type all-solid-state batteries. Herein the authors provide a brief review on recent progress in sulf...

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“…Experimentally determined and theoretically calculated activation energy barriers E a of tetrahedral lithium ion migration in lithium sulfides possessing the hcp -type sulfur anion sublattices with respect to the electronegativity of nonlithium cation element M and sulfur anion Bader charges. − Lithium sulfides in each subplot are structurally similar to the same space group. The corresponding data of E a , anion charge, and electronegativity of M are also listed in Table S2.…”

Section: Resultsmentioning

confidence: 99%

Anion Charge and Lattice Volume Maps for Searching Lithium Superionic Conductors

Zhu

2020

Chem. Mater.

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The effects of anion charge and lattice volume (lithium− anion bond length) on lithium ion migration have been investigated by utilizing the density functional theory calculations combined with the anion sublattice models. It is found that anion charge and lattice volume have great impacts on the activation energy barrier of lithium ion migration, which is validated by some reported sulfides. For the tetrahedrally occupied lithium, the less negative the anion charge is, the lower the migration energy barrier is likely to be. While for the octahedrally occupied lithium, the more negative anion charge is, the lower migration energy barrier is. Based on the full understandings of the anion sublattice model, general design strategies for developing lithium superionic conductors were proposed. Adjusting the electronegativity difference between the anion element and the nonmobile cation element by selecting the most suitable nonmobile cation element without changing the crystal structure framework can achieve low activation energy barriers for lithium ion migration. For the desired lithium superionic conductors with tetrahedrally occupied lithium, the fine nonmobile cation elements should give preference to those elements located at the right top of the periodic table of elements with large electronegativities. For the lithium superionic conductors with octahedrally occupied lithium, the fine nonmobile cation elements should give preferences to the elements located at the left bottom of the periodic table with small electronegativities.

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Computational Study of Li Ion Electrolytes Composed of Li₃AsS₄Alloyed with Li₄GeS₄

Cited by 11 publications

References 42 publications

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Design Strategies, Practical Considerations, and New Solution Processes of Sulfide Solid Electrolytes for All‐Solid‐State Batteries

Anion Charge and Lattice Volume Maps for Searching Lithium Superionic Conductors

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Computational Study of Li Ion Electrolytes Composed of Li3AsS4Alloyed with Li4GeS4

Cited by 11 publications

References 42 publications

Li4SnS4and Li4SnSe4: Simulations of Their Structure and Electrolyte Properties

Li4SnS4and Li4SnSe4: Simulations of Their Structure and Electrolyte Properties

Design Strategies, Practical Considerations, and New Solution Processes of Sulfide Solid Electrolytes for All‐Solid‐State Batteries

Anion Charge and Lattice Volume Maps for Searching Lithium Superionic Conductors

Contact Info

Product

Resources

About

Computational Study of Li Ion Electrolytes Composed of Li₃AsS₄Alloyed with Li₄GeS₄

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties