Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Kah Chun Lau Project Name: Li_air_battery Division: MSD Project title: Computational studies of Li-Air battery components Associated funding: DOE-BES Other Systems: CNM Science: Unlocking the true energy capabilities of the lithium metal (negative) electrode in a lithium battery has been mainly limited by the low capacity in intercalation and conversion reaction at the positive electrodes. However, it can be overcome by removing these electrodes and allowing lithium to react directly with oxygen in the amosphere, forming the lithium-air battery as being a hybrid battery-fuel cell system. Compared to other metal-air batteries, Zn-air and Al-air cells have aqueous electrolytes and operate at a relatively low voltage of ~1.4 V and ~1.2 V, respectively, whereas for the non-aqueous Li-air cells, it provides ~3 V and therefore yields a significantly higher specific energy. During the electrochemically reduction of oxygen, the small yet highly reactive Li cations tend to form ionic bonds in terms of lithium (per)oxides (i.e. Li2O2 and Li2O) leading to their precipitation on the electrode surfaces. These surface coverage species by the O2 reduction products passivate the electrode, shut down the reduction, and render the reaction irreversible. To advance this new technology, a systematic theoretical study of these system are therefore critically important. To date, today's battery manufacturers and developers have not yet been able to unlock the theoretical potential of Li-Air battery due to : (1) the unstable non-aqueous electrolytes that easily oxidized and decomposed during discharge/charge, thereby seriously limiting cycle life; (2) during discharge, the solid and insoluble Li2O2 and/or Li2O products are deposited on the surface or within the pores of the carbon cathode, thereby clogging the pores , restricting oxygen flow and shut down the electrical conductivity; (3) poisoning of the lithium electrode due to oxygen crossover destroys the integrity and functioning of the cell; and (4) commonly used cathode catalysts, such as metals, metal complexes, and metal oxides, do not access the full capacity of the oxygen electrode or enable sufficiently high rates. Thus in the computational studies, these problems will be addressed and explored based on state-of-the-art ab initio atomistic modeling techniques. This is a project in its 1st year that was awarded under the DOE-BES JCESR led by Argonne. Project description: Project Renewal Request: In the coming fiscal year (FY2014), we will need 1200 000 core-hour to complete our project. We will complete our current on-going work and explore different problems in Li-air batteries based on experimental input from our colleagues at ANL. To complete the current ongoing study (i.e. Li2O2 interaction on Ag_n nanoclusters catalyst/Al2O3 coated electrode), our experience indicates that 100, 000 hours is required. For our new study at FY2014, the computational methods will involve largely AIMD (CPMD, VASP) and DFT method (Gaussian09, VASP). For Gaussian09, the DFT calculation scales well up to 8 processors and for 4-8 nodes is the optimal number of nodes for geometry optimization for system size below 100 atoms. We will require about 200,000 core hours to study the Electron Paramagnetic Resonance (EPR) of O-rich Li2O2, Li2O2 and LiO2 nanoparticles, electrochemical stability and reaction paths of Li2O2 nanoparticles with DMSO and hydrophobic ionic liquids solvents against different Li salts in gas phase and solution phase. To extend our previous DFT study on Li2O2 (crystalline bulk, surfaces and clusters) system, more extensive solid phases of Li2O2/LiO2 and Li2O/Li2O2/LiO2 hetero-interfaces, grain boundaries, and amorphous phases together with the equation of states, mechanical, electronic and thermodynamic properties will be explored using DFT planewave VASP code. The VASP code is well-parallelized for 64-72 cores for 100-200 atoms system for a finite k-point calculation. For a single Γ-point calculation with a total atom ~ 300 atoms, a parallel efficiency of ~ 60% -75% can be achieved using 256 cores. Thus to explore a moderately large systems (~ 200-300 atoms), 200 000 core-hour is needed to perform the tasks. To correlate the Li-air cell with other new metal-air system (e.g. Na-air, K-air cell), the crystalline bulk and surfaces of Na-O2 and K-O2 (e.g. Na2O2, NaO2, K2O2, KO2) based on DFT calculations will be carried out using VASP code. Thus an extra 200 000 core-hour is needed. In addition, the larger system of combined electrolyte/electrode (electrolyte/Li2O2/electrode with and without metal catalyst) interfaces will be computed using CPMD and VASP code. For system involves metal surfaces and metal-catalyst (e.g. Au, Cu, Pt) that involves d-orbital electrons, the constrained-AIMD and nudge-elastic-band method implemented in VASP code and metadynamics approach based on CPMD code will be used to explore the chemical reactions. In particular, the atomistic features of electric double-layer at the metallic cathode interfaces in Li-Air battery will be systematically studied in close collaborations with experimentalist (e.g. Nenad Markovic’s group and K. Amine’s group) at Argonne. In order to have a reliable statistics and long enough simulation time, we will require about 500, 000 core hours to complete these computational intensive simulations. Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 1200000 Q1: 300000 Q2: 300000 Q3: 300000 Q4: 300000 Justification: For the details and evidence how to use the hours effectively, please see the project description and project report (FY2013). Further details of the scaling and the performance of the codes can be found as follows: (1) VASP: http://cms.mpi.univie.ac.at/vasp/vasp/Performance_parallel_code_on_various_m... (2) CPMD: http://cpmd.org/documentation (3) Gaussian09: http://www.gaussian.com/g_prod/g09_glance.htm Thank You, The LCRC Accounts System