Annealing-induced vacancy formation enables extraordinarily high Li+ ion conductivity in the amorphous electrolyte 0.33 LiI + 0.67 Li3PS4

Spannenberger, Stefan; Miß, Vanessa; Klotz, Edda; Kettner, Janosch; Cronau, Marvin; Ramanayagam, Asvitha; Capua, Francesco Di; Elsayed, Mohamed; Krause‐Rehberg, R.; Vogel, Michael; Roling, Bernhard

doi:10.1016/j.ssi.2019.115040

Cited by 30 publications

(33 citation statements)

References 40 publications

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“…Mori et al (2013) conducted both computational and experimental studies of the energy required for lithium ions to site-hop in various LPS samples and used a bond valence mismatch approach (Adams and Rao, 2009) to conclude that certain LPS compositions conduct ions more favorably owing to a lower energy penalty for crossing coordination shell boundaries . Finally, Spannenberger et al (2019) showed that the annealing of amorphous LPS electrolytes introduces "vacancies" in the non-crystalline structure which led to an increase in conductivity in the bulk. Strictly speaking, vacancies in non-crystalline materials differ from the crystalline analog due to the absence of well-defined and periodic locations in the former, but the essence of an empty site within an anionic framework which is energetically favorable for a cation is the same for both cases.…”

Section: Structure-property Relations In Lpsmentioning

confidence: 99%

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

et al. 2020

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As the need for new modalities of energy storage becomes increasingly important, allsolid-state secondary ion batteries seem poised to address a portion of tomorrow's energy needs. The success of such batteries is contingent on the solid-state electrolyte (SSE) meeting a set of material demands, including high bulk and interfacial ionic conductivity, processability with electrodes, electrode interfacial stability, thermal stability, etc. The demanding criteria for an ideal SSE has translated into decades of research devoted to discovering new electrolytes and modifying their structure/processing to improve their properties. While much research has focused on the electrolyte properties of polycrystalline ceramics, non-crystalline materials (glasses, amorphous solids, and partially crystallized materials) have demonstrated unique advantages in processability, stability, tunability, etc. These non-crystalline electrolytes are also fundamentally interesting for their potential contributions toward understanding ionic conduction in the solid state. In this review, we first review a decade of advances in two distinct families of non-crystalline lithium-ion electrolytes: lithium thiophosphate and lithium phosphate oxynitride. In doing so, we demonstrate two pathways for non-crystalline electrolytes to address the barriers toward development of all-solidstate batteries, viz., interfacial stability and conduction. Finally, we conclude with some discussion of the development of fundamental models of ionic conduction in the non-crystalline state, including the ongoing debate between strong and weak electrolyte theories. Collectively, these discussions make a promising case for the role of non-crystalline electrolytes in the next generation of energy storage technology.

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Section: Structure-property Relations In Lpsmentioning

confidence: 99%

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

et al. 2020

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“…The Bertermann et al have studied the same material, yet did not find indications for such a dimer formation [29]. If, as a hypothesis, the lifetime of such a dimer would strongly vary even for a particular material, for example due to variations of crystallite domain or grain size, grain boundaries, doping, occurrence and ratio of secondary phases, or vacancies and defects in the material [55,56], these experiments would provide a unique tool for at least an indirect assessment of existence and lifetime of Li-Li correlated motion [57]. In the present case, even though both samples were synthesized with a nominally identical route, the ratio of tetragonal-to-orthorhombic LGPS differed between 75% t-LGPS for sample 1 and 79% for sample 2.…”

Section: Resultsmentioning

confidence: 97%

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T ₁ 3D ⁷Li NMR of superionic Li₁₀GeP₂S₁₂

Paulus

Eichel

et al. 2021

Zeitschrift Für Physikalische Chemie

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The use of independent component analysis (ICA) for the analysis of two-dimensional (2D) spin-alignment echo–T 1 7Li NMR correlation data with transient echo detection as a third dimension is demonstrated for the superionic conductor Li10GeP2S12 (LGPS). ICA was combined with Laplace inversion, or discrete inverse Laplace transform (ILT), to obtain spectrally resolved 2D correlation maps. Robust results were obtained with the spectra as well as the vectorized correlation maps as independent components. It was also shown that the order of ICA and ILT steps can be swapped. While performing the ILT step before ICA provided better contrast, a substantial data compression can be achieved if ICA is executed first. Thereby the overall computation time could be reduced by one to two orders of magnitude, since the number of computationally expensive ILT steps is limited to the number of retained independent components. For LGPS, it was demonstrated that physically meaningful independent components and mixing matrices are obtained, which could be correlated with previously investigated material properties yet provided a clearer, better separation of features in the data. LGPS from two different batches was investigated, which showed substantial differences in their spectral and relaxation behavior. While in both cases this could be attributed to ionic mobility, the presented analysis may also clear the way for a more in-depth theoretical analysis based on numerical simulations. The presented method appears to be particularly suitable for samples with at least partially resolved static quadrupolar spectra, such as alkali metal ions in superionic conductors. The good stability of the ICA analysis makes this a prospect algorithm for preprocessing of data for a subsequent automatized analysis using machine learning concepts.

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“…The peak located at 81.5 ppm was assigned to amorphous PS 4 3− [39,40]. The peaks at 83.6 and 85.7 were from PS 4 3− in βand γ-Li 3 PS 4 , respectively [40]. Surprisingly, the area fraction of the amorphous phase was the highest, approximately 78%, while that of the β phase was just 15%.…”

Section: Resultsmentioning

confidence: 99%

“…The ionic conductivity and air stability of Li 3 PS 4 can also be easily tuned by the addition of different materials, i.e., oxides, nitrides and halogens. The addition of an appropriate amount of LiI into the Li 3 PS 4 structure is known to boost its ionic conductivity from approximately 5.0 × 10 −4 S cm −1 to 6.5 × 10 −4 S cm −1 [3,4]. Ambient air stability or suppression of H 2 S evolution is also improved with the existence of LiI, CuO or FeS in a Li 3 PS 4 glassy electrolyte [5,6].…”

Section: Introductionmentioning

confidence: 99%

Preparation of Li3PS4–Li3PO4 Solid Electrolytes by Liquid-Phase Shaking for All-Solid-State Batteries

Phuc¹,

Maeda²,

Yamamoto³

et al. 2021

Electronic Materials

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A solid solution of a 100Li3PS4·xLi3PO4 solid electrolyte was easily prepared by liquid-phase synthesis. Instead of the conventional solid-state synthesis methods, ethyl propionate was used as the reaction medium. The initial stage of the reaction among Li2S, P2S5 and Li3PO4 was proved by ultraviolet-visible spectroscopy. The powder X-ray diffraction (XRD) results showed that the solid solution was formed up to x = 6. At x = 20, XRD peaks of Li3PO4 were detected in the prepared sample after heat treatment at 170 °C. However, the samples obtained at room temperature showed no evidence of Li3PO4 remaining for x = 20. Solid phosphorus-31 magic angle spinning nuclear magnetic resonance spectroscopy results proved the formation of a POS33− unit in the sample with x = 6. Improvements of ionic conductivity at room temperature and activation energy were obtained with the formation of the solid solution. The sample with x = 6 exhibited a better stability against Li metal than that with x = 0. The all-solid-state half-cell employing the sample with x = 6 at the positive electrode exhibited a better charge–discharge capacity than that employing the sample with x = 0.

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Annealing-induced vacancy formation enables extraordinarily high Li+ ion conductivity in the amorphous electrolyte 0.33 LiI + 0.67 Li3PS4

Cited by 30 publications

References 40 publications

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T ₁ 3D ⁷Li NMR of superionic Li₁₀GeP₂S₁₂

Preparation of Li3PS4–Li3PO4 Solid Electrolytes by Liquid-Phase Shaking for All-Solid-State Batteries

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Annealing-induced vacancy formation enables extraordinarily high Li+ ion conductivity in the amorphous electrolyte 0.33 LiI + 0.67 Li3PS4

Cited by 30 publications

References 40 publications

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

Emerging Role of Non-crystalline Electrolytes in Solid-State Battery Research

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T 1 3D 7Li NMR of superionic Li10GeP2S12

Preparation of Li3PS4–Li3PO4 Solid Electrolytes by Liquid-Phase Shaking for All-Solid-State Batteries

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Annealing-induced vacancy formation enables extraordinarily high Li+ ion conductivity in the amorphous electrolyte 0.33 LiI + 0.67 Li3PS4

Independent component analysis combined with Laplace inversion of spectrally resolved spin-alignment echo/T ₁ 3D ⁷Li NMR of superionic Li₁₀GeP₂S₁₂