Seok-Soo Lee

The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries.

Rechargeable magnesium batteries have lately received great attention for large-scale energy storage systems due to their high volumetric capacities, low materials cost, and safe characteristic. However, the bivalency of Mg(2+) ions has made it challenging to find cathode materials operating at high voltages with decent (de)intercalation kinetics. In an effort to overcome this challenge, we adopt an unconventional approach of engaging crystal water in the layered structure of Birnessite MnO2 because the crystal water can effectively screen electrostatic interactions between Mg(2+) ions and the host anions. The crucial role of the crystal water was revealed by directly visualizing its presence and dynamic rearrangement using scanning transmission electron microscopy (STEM). Moreover, the importance of lowering desolvation energy penalty at the cathode-electrolyte interface was elucidated by working with water containing nonaqueous electrolytes. In aqueous electrolytes, the decreased interfacial energy penalty by hydration of Mg(2+) allows Birnessite MnO2 to achieve a large reversible capacity (231.1 mAh g(-1)) at high operating voltage (2.8 V vs Mg/Mg(2+)) with excellent cycle life (62.5% retention after 10000 cycles), unveiling the importance of effective charge shielding in the host and facile Mg(2+) ions transfer through the cathodes interface.

Electrochemical Behaviors of Silicon Electrode in Lithium Salt Solution Containing Alkoxy Silane Additives

The electrochemical behaviors of a silicon thin-film electrode in organic lithium salt solution were explored with focus on irreversible reactions of the first lithium charge and discharge cycling by using electrochemical quartz crystal microbalance (EQCM) combined with various electrochemical techniques. A considerable increase in mass of the silicon electrode was observed during lithium charging even before lithium absorption into the electrode, which is ascribed to the buildup of electrolyte reduction products on the silicon surface. Galvanostatic charge-discharge experiments combined with ac impedance spectroscopy demonstrate a significant overpotential growth and an aggravating capacity for the lithium charge and discharge cycling, and suggest they are due to the sedimentation of electrolyte reduction product. Additives containing alkoxy silane functional groups were evaluated as a passivation agent for lithium rechargeable batteries utilizing a silicon anode. The presence of additives in electrolyte suppressed the mass accumulation to the silicon electrode caused by irreversible electrolyte reductions and improved the electrode for cycle life. Electrochemical analyses associated with EQCM as a function of the number of alkoxy functional groups of the additives illustrate that the silicon electrode is passivated by chemical reaction of the alkoxy silane functional group of the additives with hydroxyl groups at the electrode/electrolyte interface, and this passivation improves the cycle life.

Characterization of a P2-type chelating-agent-assisted Na2/3Fe1/2Mn1/2O2 cathode material for sodium-ion batteries

A chelating-agent-assisted Na2/3Fe1/2Mn1/2O2 material is studied as a cathode for sodium-ion batteries. The addition of NH4OH results in the formation of a homogeneous powder with a lower resistance and larger carbon content on the cathode surface. The formation of a thin and stable solid-electrolyte interface layer leads to its enhanced electrochemical performance.

Effects of Ni Doping on the Initial Electrochemical Performance of Vanadium Oxide Nanotubes for Na-Ion Batteries

In this study, we demonstrated the intercalation of Na in hydrothermally synthesized VOx nanotubes (NTs) and Ni-doped VOx NTs. The changes induced in the structures of the two nanomaterials during the Na intercalation process were investigated through X-ray diffraction (XRD) analyses. It was observed that the initial capacity and rate performance of the Ni-doped VOx NTs were improved. The results of X-ray photoelectron spectroscopy (XPS) and conductance measurement confirmed that higher initial capacity and rate performance were attributed to an increase in the valence states of vanadium and increased conductivity after the Ni exchange process.

Highly reduced VOx nanotube cathode materials with ultra-high capacity for magnesium ion batteries

Here, we describe novel VOx nanotubes with vanadium at various oxidation states (V3+/V4+/V5+) as cathode materials for magnesium ion batteries. The VOx nanotubes synthesized by a microwave-assisted hydrothermal process using an amine as an organic template show a high initial discharge capacity (∼218 mA h g−1) of more than 200 mA h g−1 and an outstanding cycling performance, which have not been previously reported for magnesium ion batteries. These improvements in the electrochemical performance of our VOx nanotubes originate from the trivalent vanadium ions generated in the highly reduced VOx nanotubes. The VOx nanotubes with trivalent vanadium ions exhibit a lower charge transfer resistance at the electrode/electrolyte interfaces and superior cycling performance than the VOx nanotubes containing vanadium ions of a higher oxidation state. We first suggest that the pristine oxidation state of the vanadium ions and the maintenance of a bonding structure on the surface of the VOx nanotubes are the most important factors determining the magnesium insertion/extraction kinetics into/out of the VOx nanotubes. Our findings offer a breakthrough strategy for achieving high-energy-density magnesium rechargeable batteries using VOx nanotube cathode materials in combination with nanoarchitecture tailoring.

Aluminum Manganese Oxides with Mixed Crystal Structure: High‐Energy‐Density Cathodes for Rechargeable Sodium Batteries

We report a new discovery for enhancing the energy density of manganese oxide (Nax MnO2 ) cathode materials for sodium rechargeable batteries by incorporation of aluminum. The Al incorporation results in NaAl(0.1) Mn(0.9) O2 with a mixture of tunnel and layered crystal structures. NaAl(0.1) Mn(0.9) O2 shows a much higher initial discharge capacity and superior cycling performance compared to pristine Na(0.65) MnO2 . We ascribe this enhancement in performance to the formation of a new orthorhombic layered NaMnO2 phase merged with a small amount of tunnel Na(0.44) MnO2 phase in NaAl(0.1) Mn(0.9) O2 , and to improvements in the surface stability of the NaAl(0.1) Mn(0.9) O2 particles caused by the formation of Al-O bonds on their surfaces. Our findings regarding the phase transformation and structure stabilization induced by incorporation of aluminum, closely related to the structural analogy between orthorhombic Na(0.44) MnO2 and NaAl(0.1) Mn(0.9) O2 , suggest a strategy for achieving sodium rechargeable batteries with high energy density and stability.

Na insertion mechanisms in vanadium oxide nanotubes for Na-ion batteries.

In this study, we successfully synthesized lamellar-structured Ni0.1VOx NTs by a microwave-assisted hydrothermal method and cation exchange reaction. High initial discharge capacity and 100% efficiency were obtained when the Ni0.1VOx NTs cathode was used as a cathode material for the Na battery. The intercalation mechanism and capacity fading effect were investigated in detail both experimentally using Transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analyses and theoretically using the ab initio simulation method. During the intercalation of Na(+) into VOx NT structures, TEM, XRD, FT-IR, and XPS data revealed the cointercalation of the solvent, resulting in the expansion of the interlayer spacing and carbon and oxygen adsorption. The experimental and simulation results suggest that solvent molecules coordinated the Na insertion mechanisms into the amine interlayer during discharging. These understandings of the Na intercalation mechanism in materials based on Ni0.1VOx NTs would be useful to design more stable and high-performance VOx-based electrodes for Na battery applications.

Characterization of a thin, uniform coating on P2-type Na2/3Fe1/2Mn1/2O2 cathode material for sodium-ion batteries

A thin, uniform carbon coating on Na2/3Fe1/2Mn1/2O2 (NFMO) using 2,3-dihydroxynaphthalene (DN) was prepared. Pristine and DN-coated samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). An amorphous nanolayer coating of carbon is obtained on the surface of the layered pristine material. The 0.2 wt% DN-coated NFMO exhibits excellent electrochemical performance. An initial discharge capacity of 178 mA h g−1 was obtained at a C-rate of 0.1 C; this capacity is 20% higher than bare NFMO. Capacity retention (77.8% at the 50th cycle) is also maintained comparable to bare NFMO (77.7% at the 50th cycle). The thin and uniform carbon layer leads to improvement of charging and discharging kinetics and protects against direct contact between cathode and electrolyte.

Improving the kinetics and surface stability of sodium manganese oxide cathode materials for sodium rechargeable batteries with Al2O3/MWCNT hybrid networks

We report the design and fabrication of a novel functional material in which protective Al2O3 nanoparticles are merged with highly conductive multi-walled carbon nanotubes (MWCNTs). In this paper, we discuss in detail the effects of the Al2O3/MWCNT hybrid networks on the electrochemical performance of sodium manganese oxide (Na0.44MnO2), which is used as an electrode material in sodium rechargeable batteries. The Al2O3/MWCNT hybrid networks, which are uniformly dispersed on the surface of Na0.44MnO2, change its surface bonding nature, resulting in an improvement in the cycling performance and rate capability of Na0.44MnO2. We ascribe these enhancements in performance to the inhibition of the formation of damaging NaF-based solid-electrolyte interface (SEI) layers during cycling, which enables facile transfer of Na ions through the Na0.44MnO2 electrode/electrolyte interface. Our findings regarding the control of the chemistry and bonding structure of the Na0.44MnO2 particle surfaces induced by the introduction of the Al2O3/MWCNT functional hybrid networks provide insight into the possibilities for achieving sodium rechargeable batteries with high power density and stability.