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- Title
- NANOMATERIALS FOR ADVANCED BATTERY CATHODES
- Creator
- Moazzen, Elahe
- Date
- 2020
- Description
-
Cathode materials are key components that directly determine the power density of a battery. One of the most effective ways of developing high...
Show moreCathode materials are key components that directly determine the power density of a battery. One of the most effective ways of developing high power density cathodes is bringing them into the nano-scale world, which results in many expected and unexpected properties. Some of the desired characteristics include faster charge/discharge kinetics, improved capacity retention and structural stability due to the higher surface to volume ratio and shorter ion diffusion paths. In this dissertation a number of uniquely designed nano-sized cathode materials and nanocomposites are developed and investigated for alkaline aqueous and lithium ion battery applications. Nickel hydroxide (Ni(OH)2), which is one of the most important cathode materials in alkaline batteries, suffers from low conductivity, which usually leads to inefficient discharge and incomplete utilization of the material. A series of Ni(OH)2/Co(OH)2 core/shell nanoplatelets were synthesized and systematically investigated as cathode materials. Structure-property correlations revealed that electrochemical behavior and reversibility of Co(OH)2 redox conversion depended non-linearly on the average shell thickness, with the best performance (99.6% of theoretical capacity of the composite material) achieved at shell thickness of 1.9 ± 0.3 nm. Two fundamental phenomena were suggested to be responsible for the superior performance: templated shell deposition and galvanic coupling of core and shell materials.Manganese (IV) oxide (MnO2), which is another practical cathode that has a great potential to be utilized for a variety of energy storage systems, still has some major challenges including reversible cycling in rechargeable batteries. One of the most crucial challenges is the fact that polymorphs of MnO2 have different electrochemical activities as aqueous and Li-ion battery cathodes. However, most synthetic samples contain a mixture of polymorphs, which makes the structure-property correlations more complicated. This dissertation reports on systematic studies correlating synthesis, thermal and mechanical processing, and composite formation with polymorph composition, electrochemical performance and ion intercalation mechanisms. Among all the results, several main conclusions were reached: 1) Through control of the synthesis parameters and post-processing, desired phase compositions and nanoparticle morphologies, which optimize MnO2 performance in aqueous alkaline electrolyte, can be achieved. Nanoparticles with higher fraction of the akhtenskite polymorph showed higher reversible capacities in LiOH electrolyte (~210 mAh g-1), with stable performance for over 50 cycles. The effects of sub-nanoparticle organization of MnO2 polymorphs by thermal treatment without any morphology change on cycling performance, phase activation, and charge/discharge mechanisms in LiOH electrolyte as well as the detailed mechanism of the polymorph conversion during annealing were studied and for the first time, demonstrating that the electrochemical activity of MnO2 material strongly depends not only on the lattice structure of individual polymorphs but also on the sub-nanoparticle polymorph architecture and interphases.2) Several processing strategies, including thermal and mechanical processing, and composite fabrication were utilized to develop functional MnO2 cathodes for Li-ion batteries. Improvements in capacity and cycling performance were correlated to the presence of the pyrolusite phase of MnO2 and the crystallite size. Composite fabrication by graphene oxide wrapping also provided significant performance improvements through polymorph composition control and improved conductivity.
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- Title
- DOPING OF SODIUM CHROMIUM OXIDE CATHODE MATERIALS TO ENHANCE ELECTROCHEMICAL PERFORMANCE FOR SODIUM-ION BATTERIES
- Creator
- wang, ziyong
- Date
- 2019
- Description
-
In this project, we investigated the effects of doping several types of metals to NaCrO2 on its electrochemical performance. The doping method...
Show moreIn this project, we investigated the effects of doping several types of metals to NaCrO2 on its electrochemical performance. The doping method is aiming to stabilize the O3-type structure by partial substituting some of Cr with other metals during intercalation/deintercalation by suppressing Cr6+ migration to alkaline slab, and thus facilitate long-term cycle performance and reversible capacity. All doped NaCrO2 powders were hereby denoted to NaMe0.1Cr0.9O2 (Me=Al, Co, Ni, Mn). To achieve metal-doped NaCrO2 powders, sodium, chromium and dopant sources were mixed with various metal oxides and then subjected to 6-hour high energy ball milling, followed by heating in flow-Ar tube at 900℃ for 1 hour. Pristine NaCrO2 powder synthesized in the same process was to make comparisons with doped ones. To understand the mechanism of doping, field emission scanning microscopy (FESM) and energy Disperse Spectroscopy (EDS), as well as X-ray diffractometer (XRD), were employed to analyze the morphology and composition of final products. Benefiting from Ni doping, NaNi0.1Cr0.9O2 cell exhibited a high reversible capacity of 132 mAh g-1 at the initial cycle in a potential region between 2.0 and 3.6 V vs. Na/Na+, and 78 % of capacity retention over 70 cycles. For NaMn0.1Cr0.9O2, reversible capacity at first discharge is about 30 mAh g-1, lower than that of Ni-doped and pristine NaCrO2, while the cycle retention stays at nearly 100% after 100 cycles. The opposite charge/discharge behaviors from Ni- and Mn-doped NaCrO2 provide us a potential method for the optimization of cathode materials with the best electrochemical performance in the future.
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