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Item A Class of Organopolysulfides As Liquid Cathode Materials for High-Energy-Density Lithium Batteries(ACS, 2018) Bhargav, Amruth; Bell, Michaela Elaine; Karty, Jonathan; Cui, Yi; Fu, Yongzhu; Mechanical Engineering, School of Engineering and TechnologySulfur-based cathodes are promising to enable high-energy-density lithium–sulfur batteries; however, elemental sulfur as active material faces several challenges, including undesirable volume change (∼80%) when completely reduced and high dependence on liquid electrolyte wherein an electrolyte/sulfur ratio >10 μL mg–1 is required for high material utilization. These limit the attainable energy densities of these batteries. Herein, we introduce a new class of phenyl polysulfides C6H5SxC6H5 (4 ≤ x ≤ 6) as liquid cathode materials synthesized in a facile and scalable route to mitigate these setbacks. These polysulfides possess sufficiently high theoretical specific capacities, specific energies, and energy densities. Spectroscopic techniques verify their chemical composition and computation shows that the volume change when reduced is about 37%. Lithium half-cell testing shows that phenyl hexasulfide (C6H5S6C6H5) can provide a specific capacity of 650 mAh g–1 and capacity retention of 80% through 500 cycles at 1C rate along with superlative performance up to 10C. Furthermore, 1302 Wh kg–1 and 1720 Wh L–1 are achievable at a low electrolyte/active material ratio, i.e., 3 μL mg–1. This work adds new members to the cathode family for Li–S batteries, reduces the gap between the theoretical and practical energy densities of batteries, and provides a new direction for the development of alternative high-capacity cathode materials.Item Geometric Characteristics of Lithium Ion Battery Electrodes with Different Packing Densities(Office of the Vice Chancellor for Research, 2015-04-17) Lim, Cheolwoong; Lee, Wen Chao; Bo, Yan; Song, Zhibin; De Andrade, Vincent; De Carlo, Francesco; Kim, Youngsik; Zhu, LikunThe microstructure of electrodes plays a critical role in determining the performance of lithium ion batteries (LIBs), because the microstructure can affect the transport and electrochemical processes within electrodes (1-3). Increasing the volume fraction of active materials in the electrode will increase the energy density. However, the electrodes’ structural properties could also be changed significantly and the critical physical and electrochemical processes in LIBs will be affected. Therefore, the performance of a LIB can be optimized for a specific operating condition by designing electrode microstructures. For instance, Hellweg suggested a spatially varying porous electrode model to improve lithium ion transport in electrolyte phase at high charge/discharge rates (4). He showed that the power density of the graded porosity electrode was higher than a homogeneous porosity electrode without energy loss. In this study, we investigate the realistic geometric characteristics of electrode microstructures under different packing densities and the effect of packing density on the performance of LIBs. Moreover, a spatially varying porous electrode will be studied to increase the electrode energy density without losing rate capability. To investigate geometric characteristics of porous microstructures, cathode electrodes were fabricated from a 94:3:3 (weight %) mixture of LiCoO2 (average particle radius = 5 μm), PVDF, and super-P carbon black. To change the packing density, initial thickness of the electrodes was set in a range of 40 ~ 80 μm. Then all electrodes were pressed down to 40 μm by using a rolling press machine. A synchrotron X-ray nano-computed tomography instrument (nano-CT) at the Advanced Phothon Source of Argonne National Lab was employed to obtain morphological data of the electrodes, with a spatial resolution of 60 nm. The morphology data sets were quantitatively analyzed to characterize their geometric properties. Fig. 1 shows the porosity (ε), specific surface area (As, μm-1), tortuosity (τ), and pore size distribution of 4 different electrode microstructures. The pore size distribution of the un-pressed electrode (ε =0.56, black color) demonstrates nonuniformly dispersed active material. The highest packing density electrode (ε =0.36, red color) shows the highest tortuosity. The charge/discharge experiments were also conducted for these 4 different electrodes. The geometric properties and cell testing results will be analyzed and reported. Acknowledgments: This work was supported by US National Science Foundation under Grant No. 1335850. Fig. 1 Geometric characteristics (porosity ε, specific surface area As, tortuosity τ, pore size distribution) of xray generated porous electrode microstructure with different packing densities.