Preparation and conductivity measurements of SiS2Li2S glasses doped with LiBr and LiCl

Kennedy, John H.; Sahami, Saeed; Shea, Steven W.; Zhang, Zhengming

doi:10.1016/0167-2738(86)90142-6

Cited by 94 publications

(42 citation statements)

References 5 publications

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“…This method of postsynthesis core–shell formation minimizes structural changes to the bulk of the LGPS, allowing us to evaluate the effects of the volume constriction on stability without compositional changes in the bulk. The amorphous nature of the shell, combined with the high conductivity of the total material, suggests that the shell is a glassy sulfide . For intrinsic LGPS, the stoichiometrically expected glassy system would be 5 LiS 2 + GeS 2 + P 2 S 5 .…”

Section: Experiments and Discussionmentioning

confidence: 99%

Strain‐Stabilized Ceramic‐Sulfide Electrolytes

Fitzhugh

et al. 2019

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Among the families of solid electrolytes, sulfides retain the highest ionic conductivity. [10][11][12][13][14] Sulfide glass solid electrolytes [15,16] and glass-ceramic solid electrolytes [17][18][19] have demonstrated ionic conductivities on the order of 0.1 − 1 mS cm −1 and above 1 mS cm −1 , respectively. The ceramic-sulfide electrolytes, most notably Li 10 GeP 2 S 12 (LGPS) and Li 10 SiP 2 S 12 (LSPS), are particularly promising as they maintain exceptionally high ionic conductivities.LGPS was one of the first solid electrolytes to reach ionic conductivities comparable with liquid electrolytes [20] at 12 mS cm −1 , only to then be displaced by LSPS [10] which achieved the highest reported ionic conductivity of 25 mS cm −1 . However, despite these superior ionic conductivities, the ceramicsulfide family has been plagued by reports of narrow electrochemical stability windows [11,13,21] and interfacial reactions with common electrode materials. [4,11,22] Moreover, the reported electrochemical stability windows of ceramic-sulfides suffer from substantial inconsistencies. Several works, both computational and experimental, have shown that the ceramic-sulfides are only stable in the narrow voltage window on the order of 1.7-2.1 V versus lithium, [11][12][13]21] which is the correct general thermodynamic prediction. Many others, however, have experimentally found that the upper voltage limit can reach in excess of 4-6 V versus lithium. [10,20,23,24] A consolidated understanding of these findings is needed in order to establish design principles for practical ceramic-sulfide batteries.In this work, we develop a generalized thermodynamic theory that unifies these disparate findings and, hence, provides the unique design principle through mechano-electrochemical effect for ceramic-sulfide-based solid-state batteries. Expanding upon our previous work, [25] in which core-shell morphologies were used to widen the voltage window of LSPS, we derive a generalized strain stabilization model that indicates at which voltages strain-induced stabilization can lead to metastability of the ceramic-sulfide phases. A mean-field solution to our generalized strain model recovers our previous model [25] and is shown to be a lower limit on the strain induced stability. The second solution we explore, a nucleation or inclusion decay, is shown to provide a greater capability for stabilization. Note that our current and previous [25] understanding forms a general theoretical framework for the design of ceramic electrolyte with widened voltage stability, which is not limited to any particular design strategy, such as the core-shell morphology of Ceramic-sulfide solid electrolytes are a promising material system for enabling solid-state batteries. However, one challenge that remains is the discrepancy in the reported electrochemical stability. Recent work has suggested that it may be due to the sensitivity of ceramic sulfides to mechanically induced stability. Small changes in ceramic-sulfide microstructure, for example, have been shown to c...

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Section: Experiments and Discussionmentioning

confidence: 99%

Strain‐Stabilized Ceramic‐Sulfide Electrolytes

Fitzhugh

et al. 2019

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“…Sulfide-based electrolytes as lithium ion conductors have been investigated [1][2][3][4][5][6][7][8][9][10][11][12]. The crystals in the Li 2 S-GeS 2 -P 2 S 5 system called thio-LISICON have conductivities of 10 -4 -10 -3 S cm -1 at room temperature [5].…”

Section: Introductionmentioning

confidence: 99%

Preparation and electrochemical characterization of (100 − x)(0.7Li2S·0.3P2S5)·xLiBr glass–ceramic electrolytes

Ujiie

Hayashi

Tatsumisago

2013

Mater Renew Sustain Energy

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Glass and glass-ceramic electrolytes of (100x)(0.7Li 2 SÁ0.3P 2 S 5)ÁxLiBr (x = 0, 5, 10, 12.5, 15 and 20) (mol %) were synthesized by mechanical milling and subsequent heat treatment. Glass powders with no crystal phase were obtained by mechanical milling. The conductivities of the glasses increased concomitantly with increasing LiBr content. The conductivity at x = 20 was 3.1 9 10-4 S cm-1 at room temperature. The Li 7 P 3 S 11 crystal with high Li ion conductivity was precipitated in the glass-ceramics obtained by heat treatment. LiBr crystal was also precipitated in the glass-ceramics containing LiBr as a starting material. The glass-ceramic at x = 10 showed conductivity of 6.4 9 10-3 S cm-1. It increased to 8.4 9 10-3 S cm-1 by control of the milling period to prepare the precursor glass. 90(0.7Li 2 SÁ0.3P 2 S 5)Á10LiBr glass-ceramic with high Li ion conductivity had a wide electrochemical window of 10 V. An all-solid-state lithium secondary battery using 90(0.7Li 2 SÁ0.3P 2 S 5)Á10LiBr glassceramic as an electrolyte was charged and discharged successfully.

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“…A number of conductive lithium based sulfide glasses, which can be used as electrolytes in lithium solid state devices and batteries, have been studied in recent years. Ionic conductive glasses, with 1:1 ratio of SiS 2 -Li 2 S, doped with LiCl, LiBr and LiI was reported by Kennedy et al [3]. Maximum r is attained in these glasses when 30 mol% of lithium halide was doped.…”

Section: Introductionmentioning

confidence: 73%