Non-polar ether-based electrolyte solutions for stable high-voltage non-aqueous lithium metal batteries

Li, Zheng; Rao, Harsha; Atwi, Rasha; Sivakumar, Bhuvaneswari M.; Gwalani, Bharat; Gray, Scott; Han, Kee Sung; Everett, Thomas A.; Ajantiwalay, Tanvi A.; Vijayakumar, M.; Rajput, Nav Nidhi; Pol, Vilas G.

doi:10.1038/s41467-023-36647-1

Cited by 62 publications

(50 citation statements)

References 63 publications

(94 reference statements)

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“…These inorganic products from oxidation reactions effectively prevent the continuous oxidation of the electrolyte. 44 The physical properties of these electrolytes are listed in Figure S8 and Table S3; the ionic conductivities of the KFSI/ TMP, KFSI/TMP−DX, and KFSI/TMP−DME electrolytes were 7.38, 7.37, and 8.07 mS cm −1 , respectively. Moreover, to evaluate the stability of different electrolytes at the K metal anode, measurements were performed using asymmetric K||Cu half cells.…”

Section: Resultsmentioning

confidence: 99%

Nonfluorinated Antisolvents for Ultrastable Potassium-Ion Batteries

Wen

Zhang

et al. 2023

ACS Nano

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A robust interface between the electrode and electrolyte is essential for the long-term cyclability of potassium-ion batteries (PIBs). An effective strategy for achieving this objective is to enhance the formation of an anion-derived, robust, and stable solid−electrolyte interphase (SEI) via electrolyte structure engineering. Herein, inspired by the application of antisolvents in recrystallization, we propose a nonfluorinated antisolvent strategy to optimize the electrolyte solvation structure. In contrast to the conventional localized superconcentrated electrolyte introducing high-fluorinated ether solvent, the anion−cation interaction is considerably enhanced by introducing a certain amount of nonfluorinated antisolvent into a phosphate-based electrolyte, thereby promoting the formation of a thin and stable SEI to ensure excellent cycling performance of PIBs. Consequently, the nonfluorinated antisolvent electrolyte exhibits superior stability in the K||graphite cell (negligible capacity degradation after 1000 cycles) and long-term cycling in the K||K symmetric cell (>2200 h), as well as considerably improved oxidation stability. This study demonstrates the feasibility of optimized electrolyte engineering with a nonfluorinated antisolvent, providing an approach to realizing superior electrochemical energy storage systems in PIBs.

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Section: Resultsmentioning

confidence: 99%

Nonfluorinated Antisolvents for Ultrastable Potassium-Ion Batteries

Wen

Zhang

et al. 2023

ACS Nano

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“…ILs 45 or M n+ (TFSI -)n (M = Li, Mg, Al …) salts [46][47][48] with solvents are ubiquitous in electrochemical energy storage systems, there are no reports on quantifying the conformational proportion of TFSIin the solutions, which potentially influences the thermal/electrochemical properites of electrolytes, such as stability, interfacial capacitance and ionic conductivity. [49][50][51] We collected the Raman spectra of the solutions comprising TFSI --based ILs with polar, aprotic solvents, and quantified the impact of solvents on the population distribution of cis/trans conformers of TFSIat various concentrations.…”

Section: Solvent Effect Although the Applications Of The Electrolytes...mentioning

confidence: 99%

Dynamic hyperconjugation induced bond-angle rotation isomerization mechanism and anionic conformational rigidity-dependent melting points of ionic liquids

Yuan

Raza

Kyritsis

et al. 2023

Preprint

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The pyramidal inversion of trisubstituted heteroatoms is well-recognized. However, the stereochemistry of bicoordinated heteroatoms is poorly developed and few examples assumedly isomerize by double-torsion motion or bond-angle inversion. Here, by using ab initio molecular dynamics combined with metadynamics simulation, we reveal an unexpected competing isomerization mechanism, namely dynamic π → σ* negative hyperconjugation induced coupled rotation of bond and bond angle leads to helix inversion in bis(trifluoromethane)sulfonamide (TFSI-), making TFSI- follow four distinct trans-cis isomerization pathways with diverse energy barriers (12–52 kJ mol-1) which are significantly higher than 3.6 kJ mol-1 of sole pathway estimated by conventional static calculations. Our quantitative simulations and experiments results confirm the positive correlation between overall stability of cis-TFSI- with polarity of countercations. The melting points (Tm) of TFSI--based ionic liquids (ILs) linearly rise with the conformational rigidity of TFSI- in the ion pair state, offering a new fundamental perspective on the origin of low Tm of ILs.

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“…Fan et al developed an all-fluorinated electrolyte with a low binding ability with Li + , enabling the Li/NCA cell to work at a wide temperature range (from −95 to 125 °C). Recently, there have been many molecular engineering strategies applied to reduce the binding ability with Li + to improve the cell’s low-temperature performance. − …”

Section: Introductionmentioning

confidence: 99%

Bifunctional Localized High-Concentration Electrolyte for the Fast Kinetics of Lithium Batteries at Low Temperatures

Lai

Deng

Zhang

et al. 2023

ACS Appl. Mater. Interfaces

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Traditional lithium batteries cannot work well at low temperatures due to the sluggish desolvation process, which limits their applications in low-temperature fields. Among various previously reported approaches, solvation regulation of electrolytes is of great importance to overcome this obstacle. In this work, a tetrahydrofuran (THF)-based localized high-concentration electrolyte is reported, which possesses the advantages of a unique solvation structure and improved mobility, enabling a Li/lithium manganate (LMO) battery to cycle stably at room temperature (retains 85.9% after 300 cycles) and to work at a high rate (retains 69.0% at a 10C rate). Apart from that, this electrolyte demonstrates superior low-temperature performance, delivering over 70% capacity at −70 °C and maintaining 72.5 mAh g −1 (≈77.1%) capacity for 200 cycles at a 1C rate at −40 °C. Also, even when the rate increases to 5C, the battery could still operate well at −40 °C. This work demonstrates that solvation regulation has a significant impact on the kinetics of cells at low temperatures and provides a design method for future electrolyte design.

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Non-polar ether-based electrolyte solutions for stable high-voltage non-aqueous lithium metal batteries

Cited by 62 publications

References 63 publications

Nonfluorinated Antisolvents for Ultrastable Potassium-Ion Batteries

Nonfluorinated Antisolvents for Ultrastable Potassium-Ion Batteries

Dynamic hyperconjugation induced bond-angle rotation isomerization mechanism and anionic conformational rigidity-dependent melting points of ionic liquids

Bifunctional Localized High-Concentration Electrolyte for the Fast Kinetics of Lithium Batteries at Low Temperatures

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