Hello, A new project on the LCRC cluster has been requested. Please forward the information on to the LCRC Allocation sub-committee. Applicant's name: hakim iddir Applicant's institution: ANL Applicant's division: MSD, CNM Project Name: MBM Project title: Modeling Battery Materials (MBM) Associated funding: EFRC, EERE Other Systems: EMSL-PNNL, CNM-ANL Science: Rechargeable Li-ion batteries (LIB) have become one of the most important energy storage devices for portable electronics, electric and plug-in hybrid vehicles, owing to their high energy density and design flexibility 1. Graphitic based materials are usually used for the anode in commercial LIB because of their low cost, relatively high capacity, non-toxicity, and improved thermal stability and safety over lithium metal anodes2-5, as a result of a passivation film (solid-electrolyte interface (SEI)) that forms on graphite6. Previous studies suggested that defects in disordered/amorphous graphene sheets might be at the origin of their greatly enhanced storage capacity5,7,8. A fundamental understanding of both SEI formation, structure and properties, as well as Li and Li+ diffusion across different defects in graphene planes is a prerequisite to better understand the overall capacity and transport behavior of several graphitic anode materials and conf igurations in LIB, such as carbon nanospheres 9, carbon nanotubes (CNT)10, highly oriented pyrolitic graphite and graphene paper11. This work will be closely coupled with extensive experimental efforts conducted by two groups from the Chemical Sciences and Engineering (CSE) division, as well as research groups from Northwestern University (NU) and the University of Illinois at Urbana-Champaign (UIUC). This project is being done as part of the ANL EFRC on energy storage and an EERE funded program. (1) Tarascon, J. M.; Armand, M. Nature 2001, 414, 359. (2) Noel, M.; Santhanam, R. Journal of Power Sources 1998, 72, 53. (3) Fauteux, D.; Koksbang, R. Journal of Applied Electrochemistry 1993, 23, 1. (4) Yazami, R.; Touzain, P. Journal of Power Sources 1983, 9, 365. (5) Yoo, E.; Kim, J.; Hosono, E.; Zhou, H.-s.; Kudo, T.; Honma, I. Nano Letters 2008, 8, 2277. (6) Aurbach, D. Journal of Power Sources 2003, 119-121, 497. (7) Pan, D.; Wang, S.; Zhao, B.; Wu, M.; Zhang, H.; Wang, Y.; Jiao, Z. Chemistry of Materials 2009, 21, 3136. (8) Sato, K.; Noguchi, M.; Demachi, A.; Oki, N.; Endo, M. Science 1994, 264, 556. (9) Pol, S. V.; Pol, V. G.; Sherman, D.; Gedanken, A. Green Chemistry 2009, 11, 448. (10) Frackowiak, E.; Béguin, F. Carbon 2002, 40, 1775. (11) Abouimrane, A.; Compton, O. C.; Amine, K.; Nguyen, S. T. The Journal of Physical Chemistry C, 114, 12800. Project description: We propose to investigate the above mentioned properties (SEI formation, structure, Li transport, and reactions at the interface) on model systems using density functional theory (DFT) as implemented in the Vienna Ab Initio Simulation Package (VASP) currently available on FUSION. We have successfully investigated the growth of Li2CO3 films on graphite surfaces, as well as the diffusion of Li in Li2CO3 bulk material (TIES project). We have started to investigate the interaction of solvent molecules (EC) with both edge and basal planes of graphite, as well as Cu and Au model surfaces. During this next period we would like to continue the study of the interaction of solvent molecules with different surfaces, a work that will contribute to better understand the SEI formation and properties. This specific part of the project will be conducted in close collaboration with the group from UIUC using the Sum Generation Frequency (SFG) technique. We will partic ularly investigate the difference in interaction and diffusion properties between Li/Li+ and different graphite and graphene surfaces with several defect configurations (single, double and triple-vacancies and Stone-Wales type defect) and different types of CNT’s (semiconductor and metallic). Similar studies will be performed on Al2O3/graphite interfaces. In this case, separate MD studies will provide us with the starting structures of the interfaces that will be further optimized using VASP. This part of the project, originally proposed in TIES (2010) was not accomplished and will be proposed within this program. A total amount of 800000 hours would be necessary to complete the proposed work. Project URL: Requested allocation: 800000 Q1: 200000 Q2: 200000 Q3: 200000 Q4: 200000 Justification: The study of solvent molecules interaction with surfaces with frequency calculations will require the investigation of about 20 different configurations per solvent molecule and surface models. For each couple solvent/surface system about 50000 hours would be needed, we anticipate the investigation of at least four types of solvent molecules (EC, VC, VEC, and PC) and four different surfaces (Cu(111), Au(111) and two graphite surfaces) hence about 200000 core hours would be necessary to complete this part of the project. Li and Li+ diffusion calculations through one defect type of graphene will require about 80000 core hours. The diffusion calculations for different defects and surfaces (graphene, graphite (top and inner layers, CNT’s and Al2O3) would require about 600000 hours. A total of 800000 core hours would be needed to perform these calculations. The requester has used undetermined amount hours of their initial startup project. In addition to approving an initial amount, please specify a Category and Subcategory for this project. For a list of the current selection of approved categories, please see: https://wiki.lcrc.anl.gov/wiki/Processes/Categories Once the Allocation committee has approved the project, please go to the Project Management page to create it: https://accounts.lcrc.anl.gov/projects.php Thank You, The LCRC Accounts System