• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.72-72
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• 2012

Lithium rechargeable batteries have been widely used as key power sources for portable devices for the last couple of decades. Their high energy density and power have allowed the proliferation of ever more complex portable devices such as cellular phones, laptops and PDA's. For larger scale applications, such as batteries in plug-in hybrid electric vehicles (PHEV) or power tools, higher standards of the battery, especially in term of the rate (power) capability and energy density, are required. In PHEV, the materials in the rechargeable battery must be able to charge and discharge (power capability) with sufficient speed to take advantage of regenerative braking and give the desirable power to accelerate the car. The driving mileage of the electric car is simply a function of the energy density of the batteries. Since the successful launch of recent Ni-MH (Nickel Metal Hydride)-based HEVs (Hybrid Electric Vehicles) in the market, there has been intense demand for the high power-capable Li battery with higher energy density and reduced cost to make HEV vehicles more efficient and reduce emissions. However, current Li rechargeable battery technology has to improve significantly to meet the requirements for HEV applications not to mention PHEV. In an effort to design and develop an advanced electrode material with high power and energy for Li rechargeable batteries, we approached to this in two different length scales - Atomic and Nano engineering of materials. In the atomic design of electrode materials, we have combined theoretical investigation using ab initio calculations with experimental realization. Based on fundamental understanding on Li diffusion, polaronic conduction, operating potential, electronic structure and atomic bonding nature of electrode materials by theoretical calculations, we could identify and define the problems of existing electrode materials, suggest possible strategy and experimentally improve the electrochemical property. This approach often leads to a design of completely new compounds with new crystal structures. In this seminar, I will talk about two examples of electrode material study under this approach; $LiNi_{0.5}Mn_{0.5}O_2$ based layered materials and olivine based multi-component systems. In the other scale of approach; nano engineering; the morphology of electrode materials are controlled in nano scales to explore new electrochemical properties arising from the limited length scales and nano scale electrode architecture. Power, energy and cycle stability are demonstrated to be sensitively affected by electrode architecture in nano scales. This part of story will be only given summarized in the talk.

• Journal of the Korean Chemical Society
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• v.59 no.3
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• pp.209-214
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• 2015

The formation of complexes between SO₂ and acetic acid was studied theoretically. The ab initio and DFT calculations were performed with MP2 and B3LYP methods using 6-311++G(d,p), aug-cc-pVDZ and aug-cc-pVTZ basis sets. Six stable complexes were identified, and three stable bidentate complexes, C1, C2 and C3, were formed between SO₂ and syn-acetic acid, which is more stable form of acetic acid. Anti-acetic acid also form three complexes, C4, C5 and C6, with SO₂. C4 is bidentate and C5, C6 are monodentate complexes, which are less stable. The most stable complex, C1 has S⋯O=C and O⋯H-O interactions, and the S⋯O and O⋯H distances are less than the sum of van der Waals radii. The vibrational frequencies of complexes were calculated and were compared with those of monomers. The frequency shifts after formation of complex were found, and the overall pattern of frequency shifts relative to monomers is similar among the six complexes.

• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.1946-1952
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• 2005

New group 15 organometallic compounds, M$(phenanthrenyl)_3$ (M = P (1), Sb (2), Bi (3)) have been prepared from the reactions of 9-phenanthrenyllithium with $MCl_3$. A reaction of 9-(diphenylphosphino)phenanthrene with 2,6-diisopropylphenyl azide led to the formation of (phenanthrenyl)${(Ph)}_2P$=N-(2,6-$^iPr_2C_6H_3$) (4). The crystal structures of 2 and 4 have been determined by single-crystal X-ray diffractions, both of which crystallize with two independent molecules in the asymmetric unit. Compound 2 shows a trigonal pyramidal geometry around the Sb atom with three phenanthrenyl groups being located in a screw-like fashion with an approximately $C_3$ symmetry. A significant amount of CH- -$\pi$ interaction exists between two independent molecules of 4. The phosphorus center possesses a distorted tetrahedral environment with P-N bond lengths of 1.557(3)$\AA$ (P(1) N) and 1.532(3)$\AA$ (P(2)-N), respectively, which are short enough to support a double bond character. One of the most intriguing structural features of 4 is an unusually diminished bond angle of C-N-P, attributable to the hydrogen bonding of N(1)-H(5A) [ca. 2.49$\AA$ between two adjacent molecules in crystal packing. The compounds 1-3 show purple emission both in solution and as films at room temperature with emission maxima ($\lambda_{max}$) at 349, 366, and 386 nm, respectively, attributable to the ligand centered $\pi$ $\rightarrow$ $\pi^\ast$ transition in phenanthrene contributed by the lone pair electrons of the Gp 15 elements. Yet the nature of luminescence observed with 4 differs in that it originates from $\pi$ (diisopropylbenzene)-$\pi^\ast$ (phenanthrene) transitions with the $\rho\pi$contribution from the nitrogen atom. The emission maximum of 4 is red-shifted ranging 350-450 nm due to the internal charge transfer from the phenanthrenyl ring to the N-arylamine group as deduced from the ab initio calculations.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.41 no.6
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• pp.25-31
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• 2004

In this paper, we introduce kinetic Monte Carlo (kMC) methods for simulating diffusion process in nano-scale device fabrication. At first, we review kMC theory and backgrounds and give a simple point defect diffusion process modeling in thermal annealing after ion (electron) implantation into Si crystalline substrate to help understand kinetic Monte Carlo methods. kMC is a kind of Monte Carlo but can simulate time evolution of diffusion process through Poisson probabilistic process. In kMC diffusion process, instead of. solving differential reaction-diffusion equations via conventional finite difference or element methods, it is based on a series of chemical reaction (between atoms and/or defects) or diffusion events according to event rates of all possible events. Every event has its own event rate and time evolution of semiconductor diffusion process is directly simulated. Those event rates can be derived either directly from molecular dynamics (MD) or first-principles (ab-initio) calculations, or from experimental data.

• Journal of the Korean Chemical Society
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• v.27 no.5
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• pp.330-339
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• 1983

The CNDO/2 and STO-3G calculations were performed on nitrogen, oxygen, and sulfur compounds in order to examine the effect of interactions between two nonbonding (n) orbitals in the same molecule separated by N intervening $\sigma$ bonds based on the PMO approach. Calculated basis level energies, energy splittings, and interaction energy changes for both chain and cyclic model compounds were qualitatively compared with the corresponding predictions derived from perturbational formalism for n-n orbital interactions and successfully explained in terms of the derived energy expressions. In general, through-space interaction term could be neglected in the N and O systems. And the calculated results were explained simply by through-bond interaction term. As a result, through-bond interaction placed n- below n+ for odd systems and n+ below n- for even systems. Also energy splittings in odd systems were larger than those in even systems. However, in the cases of cis-ethylene diamine and o-phenylene diamine(conformer VI in Table 4), through-space interaction term was found to be substantial and the opposing effects of through-space and through-bonds interactions were observed. Finally it was found that the interactions between two n orbitals on S atoms always had some contribution of the destabilizing through-space interaction term. This result was consistent with the fact that the lone pair lobes of third elements were larger in size than those of the second period elements.