New nonflammable tributyl phosphate based localized high concentration electrolytes for lithium metal batteries

Feng, Xuanjie; Zhang, Zhen; Li, Rui; Xiong, Weihan; Yu, Bo; Wang, Mingshan; Chen, Junchen; Ma, Zhinyuan; Guo, Bingshu; Huang, Yun; Li, Xing

doi:10.1039/d2se00231k

Cited by 10 publications

(6 citation statements)

References 49 publications

(71 reference statements)

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“…Phosphorus‐based solvents, such as TMP and TEP, are the “first” choice for nonflammable electrolytes because the P atoms act as trapping agents for radicals, H • and OH • , that are critical for initiating combustion chain reactions, as shown in Figure 13A 189–194 . However, phosphorus‐based electrolytes do not generate stable SEI, leading to continuous electrolyte decomposition and poor CE.…”

Section: Improving the Safety Of Lmbsmentioning

confidence: 99%

“…Phosphorus-based solvents, such as TMP and TEP, are the "first" choice for nonflammable electrolytes because the P atoms act as trapping agents for radicals, H • and OH • , that are critical for initiating combustion chain reactions, as shown in Figure 13A. [189][190][191][192][193][194] 13B. 93 An SN-based dual-anion deep eutectic solution (D-DES) shows excellent nonflammability and is, therefore, suitable for design of safe electrolytes in LMBs.…”

Section: Phosphorus-based Solvents For Safe Lmbsmentioning

confidence: 99%

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Recent progress in electrolyte design for advanced lithium metal batteries

Wang

Davey

et al. 2023

SmartMat

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Lithium metal batteries (LMBs) have attracted considerable interest for use in electric vehicles and as next‐generation energy storage devices because of their high energy density. However, a significant practical drawback with LMBs is the instability of the Li metal/electrolyte interface, with concurrent parasitic reactions and dendrite growth, that leads to low Coulombic efficiency and poor cycle life. Owing to the significant role of electrolytes in batteries, rationally designed electrolytes can improve the electrochemical performance of LMBs and possibly achieve fast charge and a wide range of working temperatures to meet various requirements of the market in the future. Although there are some review papers about electrolytes for LMBs, the focus has been on a single parameter or single performance separately and, therefore, not sufficient for the design of electrolytes for advanced LMBs for a wide range of working environments. This review presents a systematic summary of recent progress made in terms of electrolytes, covering the fundamental understanding of the mechanism, scientific challenges, and strategies to address drawbacks of electrolytes for high‐performance LMBs. The advantages and disadvantages of various electrolyte strategies are also analyzed, yielding suggestions for optimum properties of electrolytes for advanced LMBs applications. Finally, the most promising research directions for electrolytes are discussed briefly.

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Section: Improving the Safety Of Lmbsmentioning

confidence: 99%

Section: Phosphorus-based Solvents For Safe Lmbsmentioning

confidence: 99%

Recent progress in electrolyte design for advanced lithium metal batteries

Wang

Davey

et al. 2023

SmartMat

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“…Unlike LP30 alone, more than 50 cycles could be completed; however, with increasing cycle number the capacity, that is, duration of each individual cycle gets increasingly shorter. It can, therefore, be said that TEP alone is not beneficial for cycling, which can most likely be attributed to reductive decomposition—this process is known for organic phosphates and usually leads to the formation of unstable SEI and poor cycling performance [55–58]. When looking at LF30–TEP (Figure 3d), this detrimental effect is not as visible at a first sight.…”

Section: Resultsmentioning

confidence: 99%

Enabling LiNO₃ in carbonate electrolytes by flame‐retardant electrolyte additive as a cosolvent for enhanced performance of lithium metal batteries

et al. 2022

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Most contemporary liquid Li‐ion battery chemistries are based on carbonate electrolytes, however, these typically perform poorly with metallic lithium. Especially, when only a small reservoir of metal is present, cells fail quickly due to the complete consumption of electrochemically active Li. Electrolyte modification is, therefore, a commonly chosen strategy to increase cycling stability and prolong lifetime of the cell. At the same time, complete redevelopment of an electrolyte usually creates a new set of problems, as conductivity, suitable electrochemical stability window and compatibility to all components of the cell needs to be ensured. It is, therefore, a reasonable strategy to alter existing electrolytes slightly, as has been done for the aforementioned carbonate electrolytes by incorporating lithium nitrate salt with triethyl phosphate as cosolvent into the mixture. As the role of the organophosphate is not fully clarified, our study aims to investigate its effect onto cycling stability, morphology, and reversibility of Li metal cycling both with and without LiNO3 salt. Using close‐to‐industrial conditions with limited excess of metallic Li at high current density, we are comparing cycling performance of the different electrolyte combinations. Contribution of the additive components to irreversible thickness growth due to the formation of inactive (“dead”) lithium and deposited lithium morphology is investigated by operando dilatometry and postmortem scanning electron microscopy. Finally, we are looking at modified solvent‐salt ratios to see whether further improvements of cell lifetime and morphology can be achieved.

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“…[40,41] Nevertheless, the application of HCE in batteries is hampered due to their high viscosity, low ionic conductivity, and high cost associated with the high amount of lithium salt employed. [42,43] In this sense, the incorporation of hydrofluoroethers (HFEs) as diluents, which are miscible with the electrolyte solvents but do not dissolve lithium salt due to their low donor number, overcome these limitations while maintaining the excellent properties of HCEs. [44] As has been widely reported in lithium-metal batteries (LMBs), SSEs demonstrate remarkable compatibility with LMA.…”

Section: Introductionmentioning

confidence: 99%

Graphene‐Based Sulfur Cathodes and Dual Salt‐Based Sparingly Solvating Electrolytes: A Perfect Marriage for High Performing, Safe, and Long Cycle Life Lithium‐Sulfur Prototype Batteries

Castillo,

Soria‐Fernández,

Rodriguez‐Peña

et al. 2023

Advanced Energy Materials

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The growing requirements for electrified applications entail exploring alternative battery systems. Lithium‐sulfur batteries (LSBs) have emerged as a promising, cost‐effective, and sustainable solution; however, their practical commercialization is impeded by several intrinsic challenges. With the aim of surpassing these challenges, the implementation of a holistic LSB concept is proposed. To this end, the effectiveness of coupling a high‐performing 2D graphene‐based sulfur cathode with a well‐suited sparingly solvating electrolyte (SSE) is reported. The incorporation of bis(fluorosulfonyl)imide (LiFSI) salt to tune sulfolane and 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropylether based SSE enables the formation of a robust and compact lithium fluoride‐rich solid electrolyte interphase. Consequently, the lithium compatibility is improved, achieving a high Coulombic efficiency (CE) of 98.8% in the Li||Cu cells and enabling thin and dense lithium depositions. When combined with a high‐performing 2D graphene‐based sulfur cathode, a symbiotic effect is shown, leading to high discharge capacities, remarkable rate capability (2.5 mAh cm−2 at C/2), enhanced cell stability, and wide temperature applicability. Furthermore, the scalability of this strategy is successfully demonstrated by assembling high‐performing monolayer prototype cells with a total capacity of 93 mAh, notable capacity retention of 70% after 100 cycles, and a high average CE of 99%.

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New nonflammable tributyl phosphate based localized high concentration electrolytes for lithium metal batteries

Abstract: Lithium metal is one of the most promising anodes for next-generation lithium batteries. However, dendrites caused by uneven deposition can pierce the separator resulting in a safety hazard. Using nonflammable...

Cited by 10 publications

References 49 publications

Recent progress in electrolyte design for advanced lithium metal batteries

Recent progress in electrolyte design for advanced lithium metal batteries

Enabling LiNO₃ in carbonate electrolytes by flame‐retardant electrolyte additive as a cosolvent for enhanced performance of lithium metal batteries

Graphene‐Based Sulfur Cathodes and Dual Salt‐Based Sparingly Solvating Electrolytes: A Perfect Marriage for High Performing, Safe, and Long Cycle Life Lithium‐Sulfur Prototype Batteries

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New nonflammable tributyl phosphate based localized high concentration electrolytes for lithium metal batteries

Abstract: Lithium metal is one of the most promising anodes for next-generation lithium batteries. However, dendrites caused by uneven deposition can pierce the separator resulting in a safety hazard. Using nonflammable...

Cited by 10 publications

References 49 publications

Recent progress in electrolyte design for advanced lithium metal batteries

Recent progress in electrolyte design for advanced lithium metal batteries

Enabling LiNO3 in carbonate electrolytes by flame‐retardant electrolyte additive as a cosolvent for enhanced performance of lithium metal batteries

Graphene‐Based Sulfur Cathodes and Dual Salt‐Based Sparingly Solvating Electrolytes: A Perfect Marriage for High Performing, Safe, and Long Cycle Life Lithium‐Sulfur Prototype Batteries

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Enabling LiNO₃ in carbonate electrolytes by flame‐retardant electrolyte additive as a cosolvent for enhanced performance of lithium metal batteries