Analysis of the structure and degree of crystallisation of 70Li2S–30P2S5 glass ceramic

Seino, Yoshikatsu; Nakagawa, Masaru; Senga, Minoru; Higuchi, Hiroyoshi; Takada, Kazunori; Sasaki, Takayoshi

doi:10.1039/c4ta04332d

Cited by 118 publications

(121 citation statements)

References 24 publications

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“…The pattern reliability factor ( R -factor) of the d-PDF was R p = 30.9% for x NMR = 30.4%. From the peak deconvolution of 31 P NMR spectra 15 , the crystallinity x NMR was calculated. As mentioned above, the peak at r = 4.1 Å is related to the order of the crystalline phase.…”

Section: Resultsmentioning

confidence: 99%

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition

Shiotani

Ohara

Tsukasaki

et al. 2017

Sci Rep

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In general, the ionic conductivity of sulfide glasses decreases with their crystallization, although it increases for a few sulphide glasses owing to the crystallization of a highly conductive new phase (e.g., Li7P3S11: 70Li2S-30P2S5). We found that the ionic conductivity of 75Li2S-25P2S5 sulfide glass, which consists of glassy and crystalline phases, is improved by optimizing the conditions of the heat treatment, i.e., annealing. A different mechanism of high ionic conductivity from the conventional mechanism is expected in the glassy phase. Here, we report the glassy structure of 75Li2S-25P2S5 immediately before the crystallization by using the differential pair distribution function (d-PDF) analysis of high-energy X-ray diffraction. Even though the ionic conductivity increases during the optimum annealing, the d-PDF analysis indicated that the glassy structure undergoes no structural change in the sulfide glass-ceramic electrolyte at a crystallinity of 33.1%. We observed the formation of a nanocrystalline phase in the X-ray and electron diffraction patterns before the crystallization, which means that Bragg peaks were deformed. Thus, the ionic conductivity in the mixture of glassy and crystalline phases is improved by the coexistence of the nanocrystalline phase.

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Section: Resultsmentioning

confidence: 99%

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition

Shiotani

Ohara

Tsukasaki

et al. 2017

Sci Rep

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“…[52]. Interestingly, purely amorphous Li 7 P 3 S 11 needs, however, to be characterized by larger activation energies in the order of 0.35 eV or higher [136]. For Li ion conductors, usually the glassy (or xray amorphous) forms represent better ion conductors than their crystalline counterparts, see, e.g., refs.…”

Section: Sulfides: LI 6 Ps 5 Br and Li 7 P 3 S 11mentioning

confidence: 99%

Ion dynamics in solid electrolytes for lithium batteries

et al. 2017

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All-solid-state batteries with ceramic electrolytes and lithium metal anodes represent an attractive alternative to conventional ion battery systems. Conventional batteries still rely on flammable liquids as electronic insulators. Despite the great efforts reported over the last years, the optimum solid electrolyte has, however, not been found yet. One of the most important properties which decides whether a ceramic is useful to work as electrolyte is ionic transport. The various time-domain nuclear magnetic resonance (NMR) techniques might help characterize and select the most suitable candidates. Together with conductivity measurements it is possible to analyze ion dynamics on different length-scales, i.e., to differentiate between local, within-site hopping processes from long-range ion transport. The latter needs to be sufficiently fast in the ceramic, in the best case competing with that of liquid electrolytes. In addition to conductivity spectroscopy, NMR can help understand the relationship between local structure and dynamic parameters. Besides information on activation energies and jump rates the data also contain suggestions about the relevant elementary steps of ion hopping and, thus, Support by the Deutsche Forschungsgemeinschaft (DFG) is highly appreciated (FOR 1277 diffusion pathways through the crystal lattice. Recent progress in characterizing ion dynamics in ceramic electrolytes by NMR relaxometry will be briefly reviewed. Focus is put on presently discussed solid electrolytes such as garnets, phosphates and sulfides, which have so far been studied in our lab.

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“…1B. , respectively (12). In previous studies, this class of electrolyte exhibits either two or three NMR peaks.…”

Section: Significancementioning

confidence: 99%

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

Villaluenga

Wujcik

Tong

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

108

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Despite high ionic conductivities, current inorganic solid electrolytes cannot be used in lithium batteries because of a lack of compliance and adhesion to active particles in battery electrodes as they are discharged and charged. We have successfully developed a compliant, nonflammable, hybrid single ion-conducting electrolyte comprising inorganic sulfide glass particles covalently bonded to a perfluoropolyether polymer. The hybrid with 23 wt% perfluoropolyether exhibits low shear modulus relative to neat glass electrolytes, ionic conductivity of 10 −4 S/cm at room temperature, a cation transference number close to unity, and an electrochemical stability window up to 5 V relative to Li + /Li. X-ray absorption spectroscopy indicates that the hybrid electrolyte limits lithium polysulfide dissolution and is, thus, ideally suited for Li-S cells. Our work opens a previously unidentified route for developing compliant solid electrolytes that will address the challenges of lithium batteries.hybrid electrolytes | inorganic sulfide glasses | fluorinated polymers | lithium batteries | lithium-sulfur batteries E lectrolytes used in lithium ion batteries that power personal electronic devices and electric vehicles comprise lithium salts dissolved in flammable organic liquids. Catastrophic battery failure often begins with the electrolyte decomposition and combustion. In addition, side reactions between the electrolyte and anode particles result in steady capacity fade. Some of the byproducts of side reactions can dissolve in the electrolyte and migrate from one electrode to the other. This effect is minimized in the case of solid electrolytes because of limited solubility and slow diffusion (1). Mixtures of liquids and salts have additional limitations. The passage of current results in an accumulation of salt in the vicinity of one electrode and depletion close to the other electrode, because only the cation participates in the electrochemical reactions. Both overconcentrated and depleted electrolytes have lower conductivity, which accentuates cell polarization and reduces power capability. Concentration polarization is absent in single-ion conductors, wherein the anions are immobilized (2). Nonflammable, single ionconducting solid electrolytes have the potential to dramatically improve safety and performance of lithium batteries (3-6).Solid electrolytes, such as inorganic sulfide glasses (Li 2 S-P 2 S 5 ), are single-ion conductors with high shear moduli (18-25 GPa) and high ionic conductivity (over 10 −4 S/cm) at room temperature (7,8). However, these materials, on their own, cannot serve as efficient electrolytes, because they cannot adhere to moving boundaries of the active particles in the battery electrode as they are charged and discharged. Hayashi et al. (9) prepared hybrid electrolytes by mixing sulfide glasses and poly(ethylene oxide) (PEO) polymers. Although the addition of PEO improves mechanical flexibility, there is a dramatic decrease in ionic conductivity because of the insulative nature of PEO. For exampl...

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Analysis of the structure and degree of crystallisation of 70Li₂S–30P₂S₅ glass ceramic

Abstract: Structural analysis of 70Li2S–30P2S5 glass ceramic by 31P MAS NMR revealed a strong correlation between the degree of crystallisation and the lithium ionic conductivity.

Cited by 118 publications

References 24 publications

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition

Ion dynamics in solid electrolytes for lithium batteries

Compliant glass–polymer hybrid single ion-conducting electrolytes for lithium batteries

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