Solution‐Processable Glass LiI‐Li<sub>4</sub>SnS<sub>4</sub> Superionic Conductors for All‐Solid‐State Li‐Ion Batteries

Park, Kern Ho; Oh, Dae Yang; Choi, Young Eun; Nam, Young Jin; Han, Lili; Kim, Ju Young; Xin, Huolin L.; Lin, Feng; Oh, Seung M.; Jung, Yoon Seok

doi:10.1002/adma.201505008

Cited by 265 publications

(261 citation statements)

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“…2 is encouraging. It is interesting to note that two other groups 6,7 have recently reported preparations of Li 4 SnS 4 using relatively low temperature processing similar to that of Kaib, Haddadpour, et al 3 Both of these studies report X-ray diffrac- tion patterns, presumably measured at room temperature, which show strong similarity to the patterns for Li 4 SnS * 4 shown in Fig. 2.…”

Section: Simulated Crystal Structuressupporting

confidence: 56%

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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: Simulated Crystal Structuressupporting

confidence: 56%

“…Sahu et al 6 showed that Li 4 SnS 4 and its alloys with Li 3 AsS 4 have reasonable ionic conductivity (10 −5 -10 −4 S/cm at room temperature) with comparatively more air-stability than other sulfide electrolytes. Park et al 7 demonstrated favorable conductivity and stability properties of Li 4 SnS 4 and its alloys with LiI.…”

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confidence: 99%

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Al-Qawasmeh

Howard

Holzwarth

2017

J. Electrochem. Soc.

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“…This gives us a hint that to improve the electrochemical performance of lithium argyrodite-based all-solid-state batteries fabrication of better interfacial contacts is essential. 34−36 …”

Section: Resultsmentioning

confidence: 99%

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Ganapathy

Hageman

et al. 2018

ACS Appl. Mater. Interfaces

158

160

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The high Li-ion conductivity of the argyrodite Li6PS5Cl makes it a promising solid electrolyte candidate for all-solid-state Li-ion batteries. For future application, it is essential to identify facile synthesis procedures and to relate the synthesis conditions to the solid electrolyte material performance. Here, a simple optimized synthesis route is investigated that avoids intensive ball milling by direct annealing of the mixed precursors at 550 °C for 10 h, resulting in argyrodite Li6PS5Cl with a high Li-ion conductivity of up to 4.96 × 10–3 S cm–1 at 26.2 °C. Both the temperature-dependent alternating current impedance conductivities and solid-state NMR spin–lattice relaxation rates demonstrate that the Li6PS5Cl prepared under these conditions results in a higher conductivity and Li-ion mobility compared to materials prepared by the traditional mechanical milling route. The origin of the improved conductivity appears to be a combination of the optimal local Cl structure and its homogeneous distribution in the material. All-solid-state cells consisting of an 80Li2S–20LiI cathode, the optimized Li6PS5Cl electrolyte, and an In anode showed a relatively good electrochemical performance with an initial discharge capacity of 662.6 mAh g–1 when a current density of 0.13 mA cm–2 was used, corresponding to a C-rate of approximately C/20. On direct comparison with a solid-state battery using a solid electrolyte prepared by the mechanical milling route, the battery made with the new material exhibits a higher initial discharge capacity and Coulombic efficiency at a higher current density with better cycling stability. Nevertheless, the cycling stability is limited by the electrolyte stability, which is a major concern for these types of solid-state batteries.

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“…In the preparation of Li PS Cl through the solution process, ethanol was used for the solvent [ 6 ]. Other solvents used to prepare solid electrolyte solutions are anhydrous hydrazine [ 7 ] (Li Ge P S , σ = 1.82 × 10 S/cm), tetrahydrofuran [ 8 ] (β Li PS , σ = 1.6 × 10 S/cm), acetonitrile [ 9 ] (Li P S I, σ = 6.3 × 10 S/cm), methylformamide [ 10 ] (Li PS , σ = 2.6 × 10 S/cm), methanol [ 11 ] (LiI Li SnS , σ = 4.1 × 10 S/cm), and ethanol [ 6 ] (Li PS Cl, σ = 1.4 × 10 S/cm). Solvents such as methanol or ethanol are more attractive to scalable procedures since they have low boiling points that allow the composite cathode to be obtained easily.…”

Section: Introductionmentioning

confidence: 99%

Effect of the binder content on the electrochemical performance of composite cathode using Li6PS5Cl precursor solution in an all-solid-state lithium battery

Rosero-Navarro

Kinoshita

Miura

et al. 2017

Ionics

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All solid state batteries with cathode composites containing high concentration of active materials are required to achieve higher energy densities. Here, a composite cathode containing up to 89 wt% of high voltage cathode active material (LiNi Mn Co O ) was prepared by covering this with a solution derived solid electrolyte (argyrodite, Li PS Cl) and the incorporation of different content binder (ethyl cellulose). All solid state batteries were fabricated using 80Li S•20P S (mol%) glass and indium metal as a solid electrolyte and anode, respectively. The all solid state battery with a composite cathode containing 0.5 wt% of ethyl cellulose showed an initial discharge capacity of 45 mAhg at 25 °C and maintained 91.7% of the discharge capacity after ten cycles, around 30% higher than that obtained for the battery with the composite cathode without a binder.

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Solution‐Processable Glass LiI‐Li₄SnS₄ Superionic Conductors for All‐Solid‐State Li‐Ion Batteries

Cited by 265 publications

References 49 publications

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte

Effect of the binder content on the electrochemical performance of composite cathode using Li6PS5Cl precursor solution in an all-solid-state lithium battery

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Solution‐Processable Glass LiI‐Li4SnS4 Superionic Conductors for All‐Solid‐State Li‐Ion Batteries

Cited by 265 publications

References 49 publications

Li4SnS4and Li4SnSe4: Simulations of Their Structure and Electrolyte Properties

Li4SnS4and Li4SnSe4: Simulations of Their Structure and Electrolyte Properties

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li6PS5Cl Solid-State Electrolyte

Effect of the binder content on the electrochemical performance of composite cathode using Li6PS5Cl precursor solution in an all-solid-state lithium battery

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Solution‐Processable Glass LiI‐Li₄SnS₄ Superionic Conductors for All‐Solid‐State Li‐Ion Batteries

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Li₄SnS₄and Li₄SnSe₄: Simulations of Their Structure and Electrolyte Properties

Facile Synthesis toward the Optimal Structure-Conductivity Characteristics of the Argyrodite Li₆PS₅Cl Solid-State Electrolyte