Predicting the Electrochemical Properties of MnO2 Nanomaterials Used in Rechargeable Li Batteries: Simulating Nanostructure at the Atomistic Level
DASSR, Cranfield University, Defence College of Management and Technology, ShriVenham, SN6 8LA UK.Journal of the American Chemical Society (Impact Factor: 12.11). 03/2009; 131(17):6161-73. DOI: 10.1021/ja8082335
Nanoporous beta-MnO2 can act as a host lattice for the insertion and deinsertion of Li with application in rechargeable lithium batteries. We predict that, to maximize its electrochemical properties, the beta-MnO2 host should be symmetrically porous and heavily twinned. In addition, we predict that there exists a "critical (wall) thickness" for MnO2 nanomaterials above which the strain associated with Li insertion is accommodated via a plastic, rather than elastic, deformation of the host lattice leading to property fading upon cycling. We predict that this critical thickness lies between 10 and 100 nm for beta-MnO2 and is greater than 100 nm for alpha-MnO2: the latter accommodates 2 x 2 tunnels compared with the smaller 1 x 1 tunnels found in beta-MnO2. This prediction may help explain why certain (nano)forms of MnO2 are electrochemically active, while others are not. Our predictions are based upon atomistic models of beta-MnO2 nanomaterials. In particular, a systematic strategy, analogous to methods widely and routinely used to model crystal structure, was used to generate the nanostructures. Specifically, the (space) symmetry associated with the nanostructure coupled with basis nanoparticles was used to prescribe full atomistic models of nanoparticles (0D), nanorods (1D), nanosheets (2D), and nanoporous (3D) architectures. For the latter, under MD simulation, the amorphous nanoparticles agglomerate together with their periodic neighbors to formulate the walls of the nanomaterial; the particular polymorphic structure was evolved using simulated amorphization and crystallization. We show that our atomistic models are in accord with experiment. Our models reveal that the periodic framework architecture, together with microtwinning, enables insertion of Li anywhere on the (internal) surface and facilitates Li transport in all three spatial directions within the host lattice. Accordingly, the symmetrically porous MnO2 can expand and contract linearly and crucially elastically under charge/discharge. We also suggest tentatively that our predictions for MnO2 are more general in that similar arguments may apply to other nanomaterials, which might expand and contract elastically upon charging/discharging.
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ABSTRACT: Central to porous nanomaterials, with applications spanning catalysts to fuel cells is their (perceived) "fragile" structure, which must remain structurally intact during application lifespan. Here, we use atomistic simulation to explore the mechanical strength of a porous nanomaterial as a first step to characterizing the structural durability of nanoporous materials. In particular, we simulate the mechanical deformation of mesoporous Li-MnO(2) under stress using molecular dynamics simulation. Specifically, such rechargeable Li-ion battery materials suffer volume changes during charge/discharge cycles as Li ions are repeatedly inserted and extracted from the host beta-MnO(2) causing failure as a result of localized stress. However, mesoporous beta-MnO(2) does not suffer structural collapse during cycling. To explain this behavior, we generate a full atomistic model of mesoporous beta-MnO(2) and simulate localized stress associated with charge/discharge cycles. We calculate that mesoporous beta-MnO(2) undergoes a volume expansion of about 16% when Li is fully intercalated, which can only be sustained without structural collapse, if the nanoarchitecture is symmetrically porous, enabling elastic deformation during intercalation. Conversely, we predict that unsymmetric materials, such as nanoparticulate beta-MnO(2), deform plastically, resulting in structural collapse of (Li) storage sites and blocked transport pathways; animations revealing elastic and plastic deformation mechanisms under mechanical load and crystallization of mesoporous Li-MnO(2) are presented at the atomistic level.
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ABSTRACT: One of the important issues in the development of new Li-ion battery technologies is to seek novel electrode materials with higher energy densities and a faster charge−discharge process. Using the first-principles calculations based on density functional theory, we systematically study the lithium interaction with the recently reported inorganic Mo12S9I9 nanowires. Eleven initial Li positions are optimized to identify the rich energetically preferable sites for Li adsorption in the nanowire at the sulfur bridge planes and on the nanowire between dressing S and I atoms. The charge density and the electronic band structure are calculated to investigate the Li−host physics. Using the climbing image nudged elastic band method, we obtain that the diffusion barrier for Li migration into the Mo12S9I9 nanowire is 0.86 eV, which is far lower than that of Li diffusion into the carbon nanotube through the sidewall (about 10 eV [Meunier et al. Phys. Rev. Lett. 2002, 88, 075506.]). These results indicate that the Mo12S9I9 nanowire will be a promising candidate material for anodes in Li-ion battery application.
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ABSTRACT: High power rechargeable lithium batteries are a key target for transport and load leveling, in order to mitigate CO(2) emissions. It has already been demonstrated that mesoporous lithium intercalation compounds (composed of particles containing nanometer diameter pores separated by walls of similar size) can deliver high rate (power) and high stability on cycling. Here we investigate how the critical dimensions of pore size and wall thickness control the rate of intercalation (electrode reaction). By using mesoporous beta-MnO(2), the influence of these mesodimensions on lithium intercalation via single and two-phase intercalation processes has been studied in the same material enabling direct comparison. Pore size and wall thickness both influence the rate of single and two-phase intercalation mechanisms, but the latter is more sensitive than the former.
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