A review on the use of carbonate-based electrolytes in Li-S batteries: A comprehensive approach enabling solid-solid direct conversion reaction

Rafie, Ayda; Kim, Jin Won; Sarode, Krishna Kumar; Kalra, Vibha

doi:10.1016/j.ensm.2022.03.015

Cited by 56 publications

(44 citation statements)

References 170 publications

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“…According to eq , such an issue will hinder the facile realization of Li–S batteries with high energy density. To combat this issue, one feasible strategy is to design sparsely solvating electrolyte to circumvent the polysulfide dissolution and thus sustain the solid-phase reaction in the lean-electrolyte condition (Figure b). − However, the main challenge lies in the sluggish SRR kinetics and large redox polarization on the grounds of the quasi-solid-state reaction route. − …”

Section: High-donor-number Componentmentioning

confidence: 99%

Kinetically Favorable Li–S Battery Electrolytes

et al. 2023

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Lithium–sulfur (Li–S) batteries suffer from rampant polysulfide shuttling and sluggish reaction kinetics, which have curtailed sulfur utilization and deteriorated their actual performance. To circumvent these detrimental issues, electrolyte engineering is a reliable strategy to control polysulfide behavior and facilitate reaction kinetics. However, the electrolyte–polysulfide nexus remains elusive, and the electrolyte design principle is far from clear, especially for pragmatic application. In this Review, key approaches to obtain kinetically favorable Li–S battery electrolytes are elucidated from three perspectives: (i) high-donor-number components, (ii) homogeneous catalysts, and (iii) endogenous co-mediators. Particular attention is paid to probing the underlying working mechanism. In addition, reaction kinetics and electrochemical performances are systematically studied, especially highlighting the strategic effectiveness of kinetically favorable Li–S battery electrolytes in lean-electrolyte conditions. This Review aims to offer meaningful guidance for the rational design of kinetically favorable electrolytes to enhance the performance and advance the commercialization of Li–S batteries.

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Section: High-donor-number Componentmentioning

confidence: 99%

Kinetically Favorable Li–S Battery Electrolytes

et al. 2023

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“…It is well‐known that the most widely‐used carbonate electrolytes have poor dynamic performance and do not match the thermodynamics of the Li‐metal anodes. It is easy for carbonate electrolytes to form a physically and chemically unstable SEI film on the surface of the Li‐metal anodes [144] . The corrosion and dendrite formation of Li are accelerated as a result of this.…”

Section: Strategies To Improving LI Metal Cycle Lifementioning

confidence: 99%

“…It is easy for carbonate electrolytes to form a physically and chemically unstable SEI film on the surface of the Li-metal anodes. [144] The corrosion and dendrite formation of Li are accelerated as a result of this. Until now, the charge-discharge Coulombic efficiency of Li-metal with conventional carbonate-based electrolytes has difficulty exceeding 98.5 %, especially under highrate cycling conditions.…”

Section: Highly Concentrated Electrolytementioning

confidence: 99%

Improvement Strategies toward Stable Lithium‐Metal Anodes for High‐Energy Batteries

Hou

Yang

Sun

et al. 2022

Batteries & Supercaps

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Lithium-metal (Li-metal) batteries are one of the most potential energy storage devices available these days. However, uncontrollable lithium dendritic growth and parasitic reactions lead to poor cycling efficiency and severe safety concerns, which restricts the use of Li-metal batteries in practical applications. This article reviews the current development status of Li-metal anodes, including investigations of reaction mechanisms and performance improvement strategies. In addition, future opportunities for developing safe and high-performance Li-metal batteries are also outlined.

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“…Indeed, a quasi-solid to solid conversion reaction has been proposed to explain SPAN’s polysulfide mitigation ability, where S 8 is directly converted to Li 2 S . The control of interface conditions has been thought to be integral to this process, and a robust CEI layer would lead to such a phenomenon .…”

Section: Introductionmentioning

confidence: 99%

“…34 Such conversion mechanisms have been proposed for SPAN batteries utilizing carbonate electrolytes, with ex-situ studies using XPS, XRF, and XANES proposing mechanisms involving the reaction of loose sulfur with carbonate electrolytes via nucleophilic attack leading to the formation of a CEI during the initial cycle. 2,15,16 Enabling quasi-solid-state behavior in ether-based electrolytes has been demonstrated using in-operando XRD by Nazar et al by tuning the solvation structure of the electrolyte. 35 Herein we propose that the presence of a robust CEI coupled with the formation and reformation of the C−S bond allows sulfur to exhibit solid−solid conversion characteristics in ether electrolytes.…”

Section: ■ Introductionmentioning

confidence: 99%

In-Operando FTIR Study on the Redox Behavior of Sulfurized Polyacrylonitrile as Cathode Material for Li–S Batteries

Pereira,

Sarode,

Rafie

et al. 2023

J. Phys. Chem. C

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Lithium−sulfur batteries have shown tremendous potential as a post lithium-ion battery chemistry, with a theoretical capacity of up to 1675 mAh/g. However, they have suffered from fundamental material challenges related to the insulating nature of the active material and discharge products as well as the solubility of intermediary products during the electrochemical reaction . One of the many proposed solutions to the latter problem has been to anchor the sulfur chain chemically to an organic molecule to form an organosulfur material. Sulfurized polyacrylonitrile (SPAN) is one such material that has shown tremendous promise. While SPAN has demonstrated long cycle life in carbonate electrolytes, its viability in ether electrolytes is only possible with the inclusion of high concentrations of lithium nitrate. To identify the chemical species present in charge and discharge cycles, elucidate the mechanisms of capacity fade, and understand why capacity is retained in the presence of lithium nitrate, we combined post-mortem analysis by XPS with an in-operando FT-IR study of three spectral regions. We probed bond vibrations we have assigned to the carbon−sulfur bond that anchors sulfur chains to the organosulfur backbone, the sulfur−sulfur bond in lithium polysulfides that evolve in electrolyte, and ring stretches of the heteropolycyclic cyclized-PAN backbone. We present evidence in support of lithiation of the heteropolycyclic backbone. We identify the formation of a robust cathode−electrolyte interphase to be a critical feature of systems with lithium nitrate present. This allows for the retention of the C−S bond and the suppression of polysulfides that otherwise cause shuttling losses.

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A review on the use of carbonate-based electrolytes in Li-S batteries: A comprehensive approach enabling solid-solid direct conversion reaction

Cited by 56 publications

References 170 publications

Kinetically Favorable Li–S Battery Electrolytes

Kinetically Favorable Li–S Battery Electrolytes

Improvement Strategies toward Stable Lithium‐Metal Anodes for High‐Energy Batteries

In-Operando FTIR Study on the Redox Behavior of Sulfurized Polyacrylonitrile as Cathode Material for Li–S Batteries

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