Hyun Deog Yoo

Mg rechargeable batteries: an on-going challenge

The first working Mg rechargeable battery prototypes were ready for presentation about 13 years ago after two breakthroughs. The first was the development of non-Grignard Mg complex electrolyte solutions with reasonably wide electrochemical windows in which Mg electrodes are fully reversible. The second breakthrough was attained by demonstrating high-rate Mg cathodes based on Chevrel phases. These prototypes could compete with lead–acid or Ni–Cd batteries in terms of energy density, very low self-discharge, a wide temperature range of operation, and an impressive prolonged cycle life. However, the energy density and rate capability of these Mg battery prototypes were not attractive enough to commercialize them. Since then we have seen gradual progress in the development of better electrolyte solutions, as well as suggestions of new cathodes. In this article we review the recent accumulated experience, understandings, new strategies and materials, in the continuous R&D process of non-aqueous Mg batteries. This paper provides a road-map of this field during the last decade.

Electrochemical and Spectroscopic Analysis of Mg2+ Intercalation into Thin Film Electrodes of Layered Oxides: V2O5 and MoO3

Electrochemical, surface, and structural studies related to rechargeable Mg batteries were carried out with monolithic thin-film cathodes comprising layered V2O5 and MoO3. The reversible intercalation reactions of these electrodes with Mg ion in nonaqueous Mg salt solutions were explored using a variety of analytical tools. These included slow-scan rate cyclic voltammetry (SSCV), chrono-potentiometry (galvanostatic cycling), Raman and photoelectron spectroscopies, high-resolution microscopy, and XRD. The V2O5 electrodes exhibited reversible Mg-ion intercalation at capacities around 150-180 mAh g(-1) with 100% efficiency. A capacity of 220 mAh g(-1) at >95% efficiency was obtained with MoO3 electrodes. By applying the electrochemical driving force sufficiently slowly it was possible to measure the electrodes at equilibrium conditions and verify by spectroscopy, microscopy, and diffractometry that these electrodes undergo fully reversible structural changes upon Mg-ion insertion/deinsertion cycling.

Impedance Analysis for Hydrogen Adsorption Pseudocapacitance and Electrochemically Active Surface Area of Pt Electrode

Electrochemically active surface area (ECA) of a polycrystalline Pt electrode is measured from the pseudocapacitance (Cp) values that are associated with hydrogen underpotential deposition. The potential-dependent Cp values are extracted from the raw impedance data by removing the interferences coming from the double-layer charging and hydrogen evolution. Three different approaches have been made: (i) by using the proportionality between the capacitance and area of the capacitive peak on imaginary capacitance plots, (ii) by complex nonlinear least-squares (CNLS) fitting on both the imaginary and real part of complex capacitance with appropriate equivalent circuits, and (iii) by using the modified Kramers-Kronig (K-K) relation. The first approach is the simplest one for the Cp measurement but cannot be used in the hydrogen evolution region (<0.05 V vs RHE), whereas the measurement can be extended down to -0.01 V with the second method. The isotherm fitting on the Cp(E) profile shows that the saturation of adsorbed hydrogen is reached at -0.1 V vs RHE. Faster data acquisition is possible with the third approach since the data analysis can be made without the time-consuming low frequency data (<100 Hz). The roughness factor and ECA of the Pt electrode are calculated from the electric charge that is obtained by integrating the potential-dependent Cp values; the roughness factor (1.4-1.5) lies within the normal range for planar electrodes.

Expanded Graphite Negative Electrode for Lithium-ion Batteries

A series of expanded graphites is prepared from graphite oxide by changing the heat-treatment temperature, and their lithiation/de-lithiation mechanism and rate performance are examined. A featureless sloping profile is observed in their charge-discharge voltage and dilatometry profiles, which is contrasted by the stepwise plateau-like profiles observed with the pristine graphite. With an increase in the heat-treatment temperature from to , the interlayer distance becomes smaller whereas the electric conductivity becomes larger, both of which are resulted from a removal of foreign atoms (mainly oxygen) from the interlayer gaps. The expanded graphite that is prepared by a heat-treatment at delivers the best rate performance, which seems to be a trade-off between the ion diffusivity that is affected by the interlayer distance and electrical conductivity.

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF3SO2)2N– at High Current Densities

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety, stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteries with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl2. Hence, ethereal solutions of Mg(TFSI)2 salt with MgCl2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm-2 and an areal capacity of ∼0.4 mAh cm-2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI- anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.