Insight on air-induced degradation mechanism of Li7P3S11 to design a chemical-stable solid electrolyte with high Li2S utilization in all-solid-state Li/S batteries

Tufail, Muhammad Khurram; Ahmad, Niaz; Zhou, Lei; Faheem, Muhammad; Yang, Le; Chen, Renjie; Yang, Wen

doi:10.1016/j.cej.2021.130535

Cited by 52 publications

(33 citation statements)

References 56 publications

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“…Coating technologies using a Li 7 P 3 S 11 slurry process have often been adopted for the preparation of cathode composites employing a broad range of metallic sulfides as the cathode active material. [ 49–53 ] In our demonstrations, we prepared TiS 2 composites by melt diffusion of excess sulfur in Li 7 P 3 S 11 SEs during the heating process ( Figure a). SEM as well as energy dispersive spectroscopy (EDS) mapping analysis of the 50TiS 2 ‐50(BM‐Li 7 P 3 S 11 ) (wt%) fabricated using a mortar and 50TiS 2 ‐50(5PS‐Li 7 P 3 S 11 ) fabricated via melt of excess sulfur are shown in Figure 7b,c, respectively.…”

Section: Resultsmentioning

confidence: 99%

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Gamo

Nishida

Nagai

et al. 2022

Adv Energy and Sustain Res

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Solution processing technology for the manufacturing of all‐solid‐state batteries (ASSBs) holds great promise of scalability and low cost over ball milling and solid‐state methods. However, conventional liquid‐phase synthesis for solid electrolytes has yet to translate into large‐scale manufacturing to address commercialization challenges. Herein, solution processing via dynamic sulfide radical anions is developed, providing rapid and scalable manufacturing of Li7P3S11 solid electrolytes (SEs). A mixture of Li2S, P2S5, and excess elemental sulfur in a mixed solvent of acetonitrile, tetrahydrofuran, and ethanol forms a homogenous precursor solution containing the S3 ·− radical anion. The presence of ethanol enhances the chemical stability of S3 ·−. The resulting sulfide radical anions serve as a mediator with two strategies: the soluble polysulfide formation and activation of P2S5, and thus allows the generation of the precursor solution in 2 min. The Li7P3S11 is prepared in 2 h without the need for ball milling or high‐energy treatment, which shows higher ionic conductivity (1.2 mS cm−1 at 25 °C) and excellent cell performance of ASSBs cells than Li7P3S11 prepared by ball milling. The solution processing technology reported here paves the way for the accelerated adoption of practical ASSBs manufacturing.

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Section: Resultsmentioning

confidence: 99%

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Gamo

Nishida

Nagai

et al. 2022

Adv Energy and Sustain Res

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“…[ 33 ] The slight oxide peak at 103.7 eV may be induced by oxidation during sample preparation/transferring. [ 34 ] After 1200 cycles, the major phase (Figure 5b) remains PS 4 3− in the P 2 p and S 2 p spectra, with only minor impurities at the Li|SE interface including slight P 2 S 7 4− and P 2 O 5 in P 2 p , [ 35 ] and Li 2 S n and Li 2 S in S 2 p . [ 14a ] This result not only confirms that the argyrodite structure well retains regardless of the reaction of metastable Cl with deposited Li but also reveals that the electrically insulated LiCl shell restrains the autochthonous local Li re‐deposition and avoids the continuous Cl16‐Si02 decomposition.…”

Section: Resultsmentioning

confidence: 99%

Metastable Decomposition Realizing Dendrite‐Free Solid‐State Li Metal Batteries

Song

Yao

et al. 2023

Advanced Energy Materials

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promising applications in energy storage devices meet the multiplying demands regarding high energy densities and safety concerns. [1] As a key part of ASSLBs, the SEs possess merits including decent thermal properties, mechanical strengths, and electrochemical stability windows; high Li transference numbers; and stable ion transports. [2] Among diverse SEs, sulfides show high ionic conductivity comparable to the commercial liquid electrolytes at room temperature, and good deformability favorable for battery assembling, [3] which are prime candidates for practical applications. [4] Nonetheless, sulfide SEs are electrochemically incompatible with metallic Li, which generates electronic conductive interphases. [5] This not only promotes the interfacial reaction of Li/sulfide causing a large interface resistance but also accelerates the Li-dendrites growth, leading to a rapid deterioration of battery performance and finally short circuits. [6] Despite the progress achieved, how to suppress Li dendrites in SEs to date is still a major issue to hinder the practical applications of lithium metal anode. Yet, no significant breakthrough has been achieved. ASSLBs using sulfide SEs and Li metal anode can only work for a few hundred cycles (<300 cycles) at room temperature, even at relatively small current densities (<0.3 mA cm −2 ), while the long-life batteries always use Li composite anodes such as Li-In, [7] Li-C, [8] and Ag-C. [4a] However, considering the high theoretical capacity (3860 mAh/g) and low electrochemical potential (−3.04 V vs SHE), Li metal remains the ultimate choice for Li batteries. [9] Moreover, a Li metal anode is important for developing next-generation Li-S batteries, [10] along with the sulfide SEs to restrain the polysulfide dissolution. It is thus significant to improve the electrochemical stability of sulfide SEs to Li. Many efforts based on external routes have been made so far to successfully mitigate the reactivity of Li/sulfide-SEs, including Li alloying (e.g., In-Li), surface decorations, construction of artificial interfaces, and incorporation of organic/ionic-liquid buffer layers. [6a,11] Combined with these external routes, if the sulfides themselves can be optimized via the intrinsic routes, for example, doping, phase transition, and microstructural modification, the interfacial stability of Li/sulfide is expected to be effectively enhanced.Compared with other sulfide-based SEs, Li-argyrodites Li 7-a PS 6-a X a (X = Cl, Br, I) as an important family member of sulfide-based SEs not only possess a low cost and high ionic A stable interface and preventing dendrite-growth are two crucial factors to realize long-life all-solid-state Li batteries (ASSLBs) using sulfide-based solid electrolytes (SEs) and Li metal anodes. But it remains a challenge to accomplish the two factors simultaneously. Here, an effective strategy is reported to realize this goal in Li-argyrodites via self-engineered metastable decomposition that is enabled by Si doping in Cl-rich argyrodites. It is shown that Cl...

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“…For instance, Li 3 N has a breakdown potential of 0.44 V, [ 61 ] while perovskite La 1/3 x Li 3 x NbO 3 SEs have a reduction potential of 1.7 V. [ 62 ] Tufail et al checked the electrochemical stability of the Li 7 P 3 S 11 SE from the Li/Li 7 P 3 S 11 /SS cell and voltage range from −0.5 to 5 V versus (Li/Li + ) at room temperature (RT) in Figure 8B. [ 17 ] The broad ESW of 0.0–5.0 V is due to the comparatively low decomposition current to prevent the large Li deposition/dissolution curve, and the traditional Li/Li 10 GeP 2 S 12 /Pt semiblocking electrode was scanned along narrow voltage windows, such as 2.5–4.0 and 0.0–2.5 V in Figure 8C,D. The current owing to the decomposition of Li 10 GeP 2 S 12 SE was clearly visible in the linear scan of the Li/Li 10 GeP 2 S 12 /Pt cell, despite the fact that the reaction current is still extremely low because of the restricted interfacial contact between SE and Pt electrode in the Li/Li 10 GeP 2 S 12 /Pt cell.…”

Section: Conventional Techniques and Fundamental Parameters For Devel...mentioning

confidence: 99%

“…Reproduced with permission. [ 17 ] Copyright 2021, Elsevier. A scanning of the Li/LGPS/Pt semiblocking electrode at a scan rate of 0.1 mV s − 1 : (C) voltage range of 0.0–2.5 V and (D) voltage range of 2.5–4.0 V. CV of Li/LGPS/LGPS–Pt/Pt semiblocking electrode at a sweep rate of 0.1 mV s − 1 : (E) voltage range of 0–2.0 V and (F) voltage range of 1.0–3.5 V. Reproduced with permission.…”

Section: Conventional Techniques and Fundamental Parameters For Devel...mentioning

confidence: 99%

Evaluation of solid electrolytes: Development of conventional and interdisciplinary approaches

Tufail,

Zhai,

Khokar

et al. 2023

Interdisciplinary Materials

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Solid‐state lithium batteries (SSLBs) have received considerable attention due to their advantages in thermal stability, energy density, and safety. Solid electrolyte (SE) is a key component in developing high‐performance SSLBs. An in‐depth understanding of the intrinsic bulk and interfacial properties is imperative to achieve SEs with competitive performance. This review first introduces the traditional electrochemical approaches to evaluating the fundamental parameters of SEs, including the ionic and electronic conductivities, activation barrier, electrochemical stability, and diffusion coefficient. After that, the characterization techniques to evaluate the structural and chemical stability of SEs are reviewed. Further, emerging interdisciplinary visualization techniques for SEs and interfaces are highlighted, including synchrotron X‐ray tomography, ultrasonic scanning imaging, time‐of‐flight secondary‐ion mass spectrometry, and three‐dimensional stress mapping, which improve the understanding of electrochemical performance and failure mechanisms. In addition, the application of machine learning to accelerate the screening and development of novel SEs is introduced. This review article aims to provide an overview of advanced characterization from a broad physical chemistry view, inspiring innovative and interdisciplinary studies in solid‐state batteries.

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Insight on air-induced degradation mechanism of Li7P3S11 to design a chemical-stable solid electrolyte with high Li2S utilization in all-solid-state Li/S batteries

Cited by 52 publications

References 56 publications

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Solution Processing via Dynamic Sulfide Radical Anions for Sulfide Solid Electrolytes

Metastable Decomposition Realizing Dendrite‐Free Solid‐State Li Metal Batteries

Evaluation of solid electrolytes: Development of conventional and interdisciplinary approaches

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