Transport and Association of Ions in Lithium Battery Electrolytes Based on Glycol Ether Mixed with Halogen-Free Orthoborate Ionic Liquid

Shah, Faiz Ullah; Гнездилов, О. И.; Gusain, Rashi; Филиппов, А. В.

doi:10.1038/s41598-017-16597-7

Cited by 33 publications

(30 citation statements)

References 48 publications

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“…[34,35] All measurements were performed from 20 to 80°C with an error of 5%. Please note that PFG-NMR method underestimates the self-diffusion coefficient [36] because it considers all the species in the system, including ion aggregates.…”

Section: Diffusivity Of the Electrolyte Ionsmentioning

confidence: 99%

Editors’ Choice—Understanding the Superior Cycling Performance of Si Anode in Highly Concentrated Phosphonium-Based Ionic Liquid Electrolyte

Araño

Mazouzi

Kerr

et al. 2020

J. Electrochem. Soc.

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Considerable effort has been devoted to improving the cyclability of silicon (Si) negative electrodes for lithium-ion batteries because it is a promising high specific capacity alternative to graphite. In this work, the electrochemical behaviour of Si in two ionic liquid (IL) electrolytes, triethyl(methyl)phosphonium bis(fluorosulfonyl)imide (P 1222 FSI) and N-propyl-Nmethylpyrrolidinium-FSI (C 3 mpyrFSI) with high and low lithium (Li) salt content is investigated at 50 °C. Results highlight that higher capacity and better cycling stability are achieved over 50 2 cycles with high salt concentration, the first time for a pyrrolidinium-based electrolyte in the area of Si negative electrodes. However, the Si cycling performance was far superior in the P 1222 FSIbased high salt content electrolyte compared to that of the C 3 mpyrFSI. To understand this unexpected result, diffusivity measurements of the IL-based electrolytes were performed using PFG-NMR, while their stability was probed using MAS-NMR and XPS after long-term cycling. A higher apparent transport number for Li ions in highly concentrated ILs, combined with a significantly lower extent of electrolyte degradation explains the superior cycle life of the highly concentrated phosphonium-based system. Si/concentrated P 1222 FSI-LiFSI/lithium nickel cobalt aluminum oxide (NCA) full cells with more than 3 mAh cm-2 nominal capacity deliver a promising cycle life and good rate capability.

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Section: Diffusivity Of the Electrolyte Ionsmentioning

confidence: 99%

Editors’ Choice—Understanding the Superior Cycling Performance of Si Anode in Highly Concentrated Phosphonium-Based Ionic Liquid Electrolyte

Araño

Mazouzi

Kerr

et al. 2020

J. Electrochem. Soc.

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“…Samples Preparation. Four ionic liquids were synthesized using methods as reported previously, [18][19][20] voltage signal (half-difference of the average lateral deflection signal on the photodetector of the forward and reverse traces, in V), was transformed into the friction force (in N) from the torsion of the cantilever. [21] Friction force data presented in this work are the average of five measurements at multiple sample positions.…”

Section: Experiments and Simulationsmentioning

confidence: 99%

Friction of Ionic Liquid–Glycol Ether Mixtures at Titanium Interfaces: Negative Load Dependence

Zhou

Zhu

et al. 2018

Adv Materials Inter

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Our atomic force microscopy (AFM) experiments and non-equilibrium molecular dynamics (NEMD) simulations have demonstrated a negative friction-load dependence to ionic liquid-glycol ether mixtures, that is, the friction decreases as the normal load increases. NEMD simulations revealed a structural reorientation of the studied ionic liquid (IL): as the normal load increases, the cation alkyl chains of ILs change the orientation to preferentially parallel to the tip scanning path. The flat-oriented IL structures, similar to the 'blooming lotus leaf', produce a new sliding interface and reduce the friction. A further molecular dynamics simulation was carried out by adopting slit pore models to mimic the tip approaching process to confirm the dynamics of ILs. We observed a faster diffusion of ILs in the smaller slit pore. The faster diffusion of ILs in the more confined slit pore, facilitates the structural reorientation of ILs. The resulted new sliding surface is responsible for the observed smaller friction at higher loads, also known as the negative friction-load dependence.These findings provide a fundamental explanation to the role of ILs in interfacial lubrications. They help to understand liquid flow properties under confinement, with implications for the development of better nanofluidic devices.

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“…[15a] Meanwhile, the peak of S-N-S at 740 cm -1 shifts up to 748 cm -1 gradually, indicating a stronger coordination of TFSIwith Li + . [21] The negative shift of the 7 Li NMR peaks also indicates the more shielding effect due to the stronger interactions between Li + and TFSI - [22] (Figure S3, Supporting Information). Notably, there is no obvious change nor new peaks emerging after introducing the TTE solvent in the Raman spectra, indicating the solvated structure is not affected by the diluent TTE.…”

Section: Resultsmentioning

confidence: 99%

Realizing Solid‐Phase Reaction in Li–S Batteries via Localized High‐Concentration Carbonate Electrolyte

Yang

et al. 2021

Advanced Energy Materials

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opment of new energy storage technologies. [1] Sulfur is an abundant, inexpensive, and environment-friendly element which can deliver a high specific capacity of 1675 mAh g -1 through its conversion mechanism. [2] Lithium-sulfur (Li-S) batteries are therefore regarded as the most promising next-generation lithium battery due to their high energy density of 2600 Wh kg -1 . [3] Although Li-S batteries have been widely studied in the past two decades, they still face many challenges in safety, performance, and lifespan for industrial commercialization. The most serious challenge is the dissolution and diffusion of lithium polysulfides (LiPSs) in conventional ether-based electrolytes. [4] The dissolved LiPSs diffuse to and chemically corrode lithium anodes, causing severe loss of active materials and rapid capacity decay. [5] Many scientists have demonstrated that chemisorption and electrocatalysis with the use of highly porous carbon, metal oxides/carbides/ sulfides/nitrides, or other polar materials are effective strategies to inhibit the shuttle effect. [5a,6] However, it should be noted that these strategies can only relieve but cannot eliminate the dissolution of LiPSs in ether solvents from a thermodynamic point of view. [7] Enabling a solid-phase conversion mechanism of sulfur could help avoid the production of soluble intermediate LiPSs. Several studies have demonstrated that carbonate-based Li-S batteries using sulfurized polyacrylonitrile (S@pPAN) or microporouscarbon/small-sulfur cathodes show enhanced safety and stable cycling performance by eliminating the production of LiPSs. [8] The carbonate-based electrolytes possess high ionic conductivity, wide electrochemical window, high volatilization temperature, are commercially mature, and have wide application, showing great promise for replacing ether-based electrolytes in Li-S batteries. [9] Unfortunately, most sulfur cathodes are chemically incompatible with carbonate-based solvents due to the irreversible nucleophilic attack at carbonyl carbon atoms by LiPSs. However, some sulfur cathodes can be paired with carbonate electrolytes if the cathodes have small sulfur molecules confined within a microporous structure or strongly chemically bonded to a polymeric host, which will limit the sulfur mass content (<50 wt%) and areal loading in cathodes, thereby compromising energy density. [10] A molecular layer deposition Lithium-sulfur (Li-S) batteries have attracted significant attention because of their high theoretical energy density and low cost. However, their poor cyclability caused by the shuttle effect in ether-based electrolytes remains a great challenge for their practical application. Herein, a novel electrolyte is proposed by combining widely used carbonate solvents diethyl carbonate/fluoroethylene carbonate and inert diluent 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether for Li-S batteries based on typical mesoporous carbon/sulfur (KB/S) materials. Differing from the conventional dissolution-precipitation mechanism, the sulfur cathodes ...

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Transport and Association of Ions in Lithium Battery Electrolytes Based on Glycol Ether Mixed with Halogen-Free Orthoborate Ionic Liquid

Cited by 33 publications

References 48 publications

Editors’ Choice—Understanding the Superior Cycling Performance of Si Anode in Highly Concentrated Phosphonium-Based Ionic Liquid Electrolyte

Editors’ Choice—Understanding the Superior Cycling Performance of Si Anode in Highly Concentrated Phosphonium-Based Ionic Liquid Electrolyte

Friction of Ionic Liquid–Glycol Ether Mixtures at Titanium Interfaces: Negative Load Dependence

Realizing Solid‐Phase Reaction in Li–S Batteries via Localized High‐Concentration Carbonate Electrolyte

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