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Crystal structure and cation-anion interactions of potassium (Difluoromethanesulfonyl) (trifluorome thanesulfonyl)imide.

ABSTRACT: Sulfonimide salts are of great interest for battery use thanks to their special properties including sufficient superior chemical/thermal stabilities, structural flexibility, etc. In particular, the hydrogen-containing sulfonimide (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide anion {[N(SO₂CF₂H) (SO₂CF₃)]^-, DFTFSI^-}, stands out owing to its suppressed anion mobility and superior electrochemical properties. We herein report the structural analyses of potassium (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide {K [N(SO₂CF₂H) (SO₂CF₃)], KDFTFSI} by virtue of single crystal X-ray diffraction and computational approaches. Our results reveal that KDFTFSI crystallizes in a orthorhombic cell (space group: Pbcn) comprising of cationic and anionic layers, which is similar to the conventional sulfonimide salt, potassium bis(trifluoromethanesulfonyl)imide {K [N(SO₂CF₃)₂], KTFSI}. Gas-phase density functional theory calculations show that the conversion from trans to cis DFTFSI^- anions is hindered due to the presence of stabilizing intramolecular H-bonding interactions in the trans conformer; yet interaction with K⁺ substantially minimizes the energy difference between the two conformers due to the formation of strong tridentate K⁺ coordination with oxygen atoms in the cis KDFTFSI. This work is anticipated to provide further understanding on the structure-property relations of hydrogenated sulfonimide anions, and thus inspire the structural design of new anions for battery research.

SUBMITTER: Sanchez-Diez E

PROVIDER: S-EPMC10368979 | biostudies-literature | 2023

REPOSITORIES: biostudies-literature

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Crystal structure and cation-anion interactions of potassium (Difluoromethanesulfonyl) (trifluorome thanesulfonyl)imide.

Sánchez-Diez Eduardo E Garcia Lorena L Arcelus Oier O Qiao Lixin L San Felices Leire L Carrasco Javier J Armand Michel M Martínez-Ibañez Maria M Zhang Heng H

Frontiers in chemistry 20230712

Sulfonimide salts are of great interest for battery use thanks to their special properties including sufficient superior chemical/thermal stabilities, structural flexibility, etc. In particular, the hydrogen-containing sulfonimide (difluoromethanesulfonyl)(trifluoromethanesulfonyl)imide anion {[N(SO2CF2H) (SO2CF3)]-, DFTFSI-}, stands out owing to its suppressed anion mobility and superior electrochemical properties. We here ...[more]

PMID: 37502234

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Project description:ConspectusResearch at historically black colleges and universities (HBCUs) started with humble beginnings by G. W. Carver at Tuskegee Institute AL, the nation's first HBCU. He is now remembered as the man who transformed one crop, peanuts to more than 300 useful products such as food, beverages, medicines, cosmetics, and chemicals. However, research was not the focus of most of the newly founded HBCUs to provide, primarily, liberal arts education and training in agriculture for the black minority. HBCUs remained segregated, lacking facilities such as libraries and scientific/research equipment comparable to those at traditionally white institutions. While the Civil Rights Act of 1964 heralded the dawn of "equal opportunity" and progressive desegregation in the South, many public HBCUs had to close or merge with white institutions due to loss of funding and/or students. In order to remain competitive in enrollment and financial support of the best talents, HBCUs have been expanding their research and federal contracts by working in collaboration with research-intensive institutions and/or minority-serving institutions (MSIs). Albany State University (ASU), an HBCU with a great tradition of in-house and extramural undergraduate research, has partnered with the laboratory of Dr. John Miller at Brookhaven National Laboratory (BNL) to offer the best training and mentorship to our undergraduates. Students synthesized and performed conductivity measurements on a new generation of ion-pair salts. One of these constitutes, potentially, a nonaqueous electrolyte for the next generation of high-energy-density batteries owing to its electrochemical properties.The quest for rechargeable batteries with greater energy density and capable of shorter recharge time at the "pump" for electrical vehicles (EVs) is leading the development of electrolytes with higher ionic mobility and greater limiting conductivity. In order to achieve high energy density, it is vital for an electrolyte to be electrochemically stable while operating at high voltages.The development of a weakly coordinating anion/cation electrolyte for energy storage applications offers a challenge of technological significance. This class of electrolytes is advantageous for the investigation of electrode processes in low-polarity solvents. The improvement arises from the optimization of both ionic conductivity and solubility of the ion pair formed between a substituted tetra-arylphosphonium (TAPR) cation and tetrakis-fluoroarylborate (TFAB), a weakly coordinating anion. The chemical "push-pull" between cation and anion affords a highly conducting ion pair in low-polarity solvents such as tetrahydrofuran (THF) and tert-butyl methyl ether (TBME). The limiting conductivity value of the salt, namely, tetra-p-methoxy-phenylphosphonium-tetrakis(pentafluorophenyl)borate or TAPR/TFAB (R = p-OCH3), is in the range of lithium hexafluorophosphate (LiPF6) used in lithium-ion batteries (LIBs). This TAPR/TFAB salt can improve the efficiency and stability of batteries over those of existing and commonly used electrolytes by optimizing the conductivity tailored to the redox-active molecules. LiPF6 dissolved in carbonate solvents is unstable with high-voltage electrodes that are required to achieve greater energy density. In contrast, the TAPOMe/TFAB salt is stable and has a good solubility profile in low-polarity solvents given its relatively great size. And it constitutes a low-cost supporting electrolyte capable of bringing nonaqueous energy storage devices to compete with existing technologies.

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Dataset Information

Crystal structure and cation-anion interactions of potassium (Difluoromethanesulfonyl) (trifluorome thanesulfonyl)imide.

Publications

Crystal structure and cation-anion interactions of potassium (Difluoromethanesulfonyl) (trifluorome thanesulfonyl)imide.

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