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On the Beneficial Effect of MgCl₂ as Electrolyte Additive to Improve the Electrochemical Performance of Li₄Ti₅O12 as Cathode in Mg Batteries.

ABSTRACT: Magnesium batteries are a promising technology for a new generation of energy storage for portable devices. Attention should be paid to electrolyte and electrode material development in order to develop rechargeable Mg batteries. In this study, we report the use of the spinel lithium titanate or Li₄Ti₅O12 (LTO) as an active electrode for Mg2+-ion batteries. The theoretical capacity of LTO is 175 mA h g-1, which is equivalent to an insertion reaction with 1.5 Mg2+ ions. The ability to enhance the specific capacity of LTO is of practical importance. We have observed that it is possible to increase the capacity up to 290 mA h g-1 in first discharge, which corresponds to the reaction with 2.5 Mg2+ ions. The addition of MgCl₂·6H₂O to the electrolyte solutions significantly improves their electrochemical performance and enables reversible Mg deposition. Ex-situ X-ray diffraction (XRD) patterns reveal little structural changes, while X-ray photoelectron spectrometer (XPS) (XPS) measurements suggest Mg reacts with LTO. The Ti3+/Ti4+ ratio increases with the amount of inserted magnesium. The impedance spectra show the presence of a semicircle at medium-low frequencies, ascribable to Mg2+ ion diffusion between the surface film and LTO. Further experimental improvements with exhaustive control of electrodes and electrolytes are necessary to develop the Mg battery with practical application.

SUBMITTER: Cabello M

PROVIDER: S-EPMC6474089 | biostudies-other | 2019 Mar

REPOSITORIES: biostudies-other

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On the Beneficial Effect of MgCl₂ as Electrolyte Additive to Improve the Electrochemical Performance of Li₄Ti₅O12 as Cathode in Mg Batteries.

Cabello Marta M Ortiz Gregorio F GF Lavela Pedro P Tirado José L JL

Nanomaterials (Basel, Switzerland) 20190326 3

Magnesium batteries are a promising technology for a new generation of energy storage for portable devices. Attention should be paid to electrolyte and electrode material development in order to develop rechargeable Mg batteries. In this study, we report the use of the spinel lithium titanate or Li₄Ti₅O12 (LTO) as an active electrode for Mg2+-ion batteries. The theoretical capacity of LTO is 175 mA h g-1, which is equivalent to an insertion reaction with 1.5 Mg<s ...[more]

PMID: 30917592

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Project description:Fluorinated electrolytes based on fluoroethylene carbonate (FEC) have been considered as promising alternative electrolytes for high-voltage and high-energy capacity lithium-ion batteries (LIBs). However, the compatibility of the fluorinated electrolytes with graphite negative electrodes is unclear. In this paper, we have systematically investigated, for the first time, the stability of fluorinated electrolytes with graphite negative electrodes, and the result shows that unlike the ethylene carbonate (EC)-based electrolyte, the FEC-based electrolyte (EC was totally replaced by FEC) is incapable of forming a protective and effective solid electrolyte interphase (SEI) that protects the electrolyte from runaway reduction on the graphite surface. The reason is that the lowest unoccupied molecular orbital energy levels are also lowered by the introduction of fluorine into the solvent, and the FEC solvent has poorer resistance against reduction, leading to instability on the graphite negative electrode. To tackle this problem, two lithium salts of lithium bis(oxalato)borate and lithium difluoro(oxalato)borate (LiDFOB) have been investigated as negative-electrode film-forming additives. Incorporation of only 0.5 wt % LiDFOB to a FEC-based electrolyte [1.0 M LiPF6 in 3:7 (FEC-ethyl methyl carbonate)] results in excellent cycling performance of the graphite negative electrode. This improved property originates from the generation of a thinner and better quality SEI film with little LiF by the sacrificial reduction of the LiDFOB additive on the graphite negative electrode surface. On the other hand, this additive can stabilize the electrolyte by scavenging HF. Meanwhile, the incorporated LiDFOB additive has positive influence on the interphase layer on the positive electrode surface and significantly decreases the amount of HF formation, finally leading to improved cycling stability and rate capability of LiNi0.5Mn1.5O4 electrodes at a high cutoff voltage of 5 V. The data demonstrate that the LiDFOB additive not only exhibits a superior compatibility with graphite but also improves the electrochemical properties of high-voltage spinel LiNi0.5Mn1.5O4 positive electrodes considerably, confirming its potential as a prospective, multifunctional additive for 5 V fluorinated electrolytes in high-energy capacity lithium-ion batteries (LIBs).

Dataset Information

On the Beneficial Effect of MgCl₂ as Electrolyte Additive to Improve the Electrochemical Performance of Li₄Ti₅O12 as Cathode in Mg Batteries.

Publications

On the Beneficial Effect of MgCl₂ as Electrolyte Additive to Improve the Electrochemical Performance of Li₄Ti₅O<sub>12</sub> as Cathode in Mg Batteries.

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