Performance evaluation and characterization of lithium-ion cells under simulated PHEVs' drive cycles
In PHEVs, batteries operate under charge sustaining and charge depleting mode based on torque requirement and state of charge. In the current article, 26650 lithium-ion cells were cycled extensively at 25 and 50 oC under charge sustaining mode to monitor capacity and cell impedance values followed by analyzing the Lithium iron phosphate (LiFePO4) cathode material by X-ray diffraction analysis (XRD). High frequency resistance measured by electrochemical impedance spectroscopy was found to increase significantly under high temperature cycling, leading to power fading. No phase change in LiFePO4 cathode material is observed after 330 cycles at elevated temperature under charge sustaining mode from the XRD analysis. However, there was significant change in crystallite size of the cathode active material after charge/discharge cycling with charge sustaining mode. Additionally, 18650 lithium-ion cells were tested under charge depleting mode to monitor capacity values.
In this study, development of electrochemical reactor, characterization of membrane electrode assembly (MEA) and analysis of electrochemical reduction of carbon dioxide (ERC) is discussed. Electrodes using various catalyst materials in solid polymer based electrolyte (SPE) along with gas diffusion layer (GDL) are developed. The prepared membrane electrodes are characterized under ex-situ conditions using scanning electron microscopy (SEM). The membranes are later placed in the electrochemical reactor for the in-situ characterization to assess the performance of the membrane electrode assembly.
The electrodes are processed by airbrushing the metal particles on the nafion membrane and then are electrochemically characterized by linear sweep voltammetry. The anode was kept constant with platinum whereas the cathode was examined with compositions of different metal catalysts. The products formed subsequently are analyzed using gas chromatography (GC) and Residual gas analysis (RGA). Hydrogen (H2) and carbon monoxide (CO) are detected using GC while the hydrocarbons are detected by performing quantitative analysis using RGA. The preliminary experiments gave very encouraging results. However, more work needs to be done to achieve new heights.
The capacity degradation rate under the PHEV test protocol for batteries with NMC-based cathode (16% over 800 cycles) was twice the degradation compared to batteries with LFP-based cathode (8% over 800 cycles), reiterating the fact that batteries with LFP cathodes have a higher cycle life compared to other lithium battery chemistries. Also, the high frequency resistance measured by electrochemical impedance spectroscopy (EIS) was found to increase significantly with cycling, leading to power fading for both the NMC- as well as LFP-based batteries. The active materials analyzed using X-ray diffraction (XRD) showed no significant phase change in the materials after 800 PHEV cycles. For second-life tests, these batteries were subjected to a constant charge-discharge cycling procedure to analyze the capacity degradation and materials characteristics.
Nanomaterials enabled technologies have been seamlessly integrated into applications such as aviation and space, chemical industry, optics, solar hydrogen, fuel cell, batteries, sensors, power generation, aeronautic industry, building/construction industry, automotive engineering, consumer electronics, thermoelectric devices, pharmaceuticals, and cosmetic industry. Clean energy and environmental applications often demand the development of novel nanomaterials that can provide shortest reaction pathways for the enhancement of reaction kinetics. Understanding the physicochemical, structural, microstructural, surface, and interface properties of nanomaterials is vital for achieving the required efficiency, cycle life, and sustainability in various technological applications. Nanomaterials with specific size and shape such as nanotubes, nanofibers, nanowires, nanocones, nanocomposites, nanorods, nanoislands, nanoparticles, nanospheres, and nanoshells to provide unique properties can be synthesized by tuning the process conditions.
Various biologically inspired flow field designs of the gas distributor (interconnector) have been designed and simulated. Their performance using Nafion-212 with humidified H2 and Air at 80 °C with the ANSYS Fluent Fuel Cell module software was evaluated. Novel interdigitated designs were optimized by obeying biologically inspired branching rules. These rules allow for more mathematically formal descriptions of flow field designs, enabling relatively simple optimization. The channel to land ratio was kept equivalent between designs with typical values between 0.8 and 1.0. The pressure drop and the current density distribution were monitored for each design on both anode and cathode sides. The most promising designs are expected to exhibit lower pressure drop however, low pressure drop can also be an indication of potential water flooding at higher operating current density. A biologically inspired interdigitated design with 9 inlet channels exhibited reduced pressure drop and improved current density distribution compared to all other interdigitated designs evaluated in this study. The simulated fuel cell performance data at ambient pressure with humidified H2 and air compares well with the experimental data using a single serpentine flow field design.
Zeolitic Imidazolate Frameworks (ZIFs) are one of the potential candidates as highly conducting networks with surface area with a possibility to be used as catalyst support. In the present study, highly active state-of-the-art Pt-NCNTFs catalyst was synthesized by pyrolyzing ZIF-67 along with Pt precursor under flowing Ar-H2 (90-10 %) gas at 700 °C. XRD analysis indicated the formation of Pt-Co alloy on the surface of the nanostructured catalyst support. The high resolution TEM examination showed the particle size range of 7 to 10 nm. Proton exchange membrane fuel cell performance was evaluated by fabricating membrane electrode assemblies using Nafion-212 electrolyte using H2/O2 gases (100 % RH) at various temperatures. The peak power density of 630 mW.cm2 was obtained with Pt-NCNTFs cathode catalyst and commercial Pt/C anode catalyst at 70 °C at ambient pressure.
The current Solid-State Electrolyte (SSE) used in Li-ion batteries are limited by their current production methods (i.e., die-pressing; tape casting), planar geometries and random porosities. This constrains their use for mass production in manufacturing plants. 3D-printing of SSEs, however, is a new, highly-researched method that shows promise in expanding beyond the laboratory to more large-scale industrial production as rapid prototyping takes place. Indeed, laboratory studies to date suggest that SSE technology is safer than current production methods and provides a safe high energy solid-state battery. For SSE technology to become a reality though, it must be scalable and financially feasible. Therefore, this thesis aids to bridge the gap between laboratory studies and commercialization by examining the financial feasibility of adopting this technology for a hypothetical battery manufacturing plant. In doing this, I develop a model of the incremental net cash flows, and subsequently the Net Present Value (NPV), from such an enterprise. If the present value of future cash flows from the enterprise are anticipated to be greater than the investment costs, the NPV is positive and the investment in this new technology would be considered instantaneously value enhancing and thus financially feasible. However, future cash flows are highly uncertain, which brings into question financial feasibility in a risky environment. To address the riskiness of future cash flows, I model three risk factors: the cost of raw materials, the potential growth in battery sales, as well as the potential mark-up (profit margin) of the SSE enterprise. Using Monte Carlo simulation (MCS) I model the incremental cash flows considering these risk factors and derive probabilistic assessments of NPV. My analysis suggests that despite the uncertainty caused by the volatility of raw metal prices, assumptions on price mark-up, and uncertain market demand for Li-ion batteries, there is a high probability of an investment in SSE batteries being financially feasible. Future research should consider the value of real options (optionality embedded in tangible investments) as traditional NPV analysis may underestimate the potential value of an investment in the presence of uncertain cash flows, especially if management has the ability to respond to the uncertainty.
