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Calcium and phosphate are essential electrolytes in the human body, with calcium being the most abundant mineral. Around 99% of the body's calcium is stored in the skeleton and teeth, forming a crystal lattice of mineral salts in combination with phosphates. Calcium plays crucial roles in various bodily functions such as blood clotting, neurotransmitter release, muscle tone maintenance, and nervous and muscle tissue excitability.
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Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
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Salts with Acidic Ions
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Fluorinated alkyl-phosphate-based electrolytes with controlled lithium-ion coordination structure.

Saki Sawayama1, Yanko M Todorov1, Hideyuki Mimura2

  • 1Graduate School of Sciences and Technology for Innovation, Yamaguchi University, 2-16-1 Tokiwadai, Ube, Yamaguchi 755-8611, Japan. k-fujii@yamaguchi-u.ac.jp.

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Summary

We developed novel Li-ion electrolytes using tris(2,2,2-trifluoroethyl)phosphate (TFEP) and lithium bis(fluorosulfonyl)amide (LiFSA) that enable efficient Li-ion insertion into graphite anodes. Adding acetonitrile improved Li-ion coordination and facilitated successful battery cycling.

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Area of Science:

  • Electrochemistry
  • Materials Science
  • Chemical Engineering

Background:

  • Developing stable and high-performance electrolytes is crucial for advancing lithium-ion batteries.
  • Non-flammable solvents are desirable for enhanced battery safety.
  • Understanding Li-ion solvation structures is key to optimizing electrolyte performance.

Purpose of the Study:

  • To propose and investigate novel Li-ion solvation-controlled electrolytes based on tris(2,2,2-trifluoroethyl)phosphate (TFEP) and lithium bis(fluorosulfonyl)amide (LiFSA).
  • To elucidate the molecular-level solvation structures of Li-ions in TFEP-based electrolytes.
  • To evaluate the impact of electrolyte structure on Li-ion insertion/deinsertion in graphite anodes.

Main Methods:

  • Infrared (IR) and Raman spectroscopy for structural analysis.
  • High-energy X-ray total scattering (HEXTS) for detailed structural insights.
  • Molecular dynamics (MD) simulations to model Li-ion coordination.
  • Electrochemical testing of Li-ion insertion/deinsertion in graphite electrodes.

Main Results:

  • Identified [Li(TFEP)2(bi-FSA)] as the major Li-ion species in binary LiFSA/TFEP electrolytes (<1.0 mol dm⁻³).
  • Demonstrated that acetonitrile (AN) addition alters Li-ion coordination to a mono-FSA mode by solvating Li-ions.
  • Achieved successful Li-ion insertion/deinsertion in graphite anodes using 1.0 mol dm⁻³ LiFSA/TFEP with AN, unlike electrolytes without AN.

Conclusions:

  • Li-ion solvation structure significantly influences graphite anode performance.
  • The weaker Li+-mono-FSA- interactions in the AN-containing electrolyte facilitate easier de-coordination, promoting charge transfer and Li-ion cycling.
  • TFEP-based electrolytes with LiFSA and AN offer a promising avenue for developing safer and more efficient lithium-ion batteries.