Engineering Papers⌕ Search

Engineering topics

Thomsen, Edwin C.

Publications and source records attributed to Thomsen, Edwin C..

Investigation of Fe-Ni Battery/Module for Grid Service Duty Cycles

Iron–nickel (Fe-Ni) batteries are renowned for their durability and resilience against overcharging and operating temperatures. However, they encounter challenges in achieving widespread adoption for energy storage applications due to their low efficiency and the need for regular maintenance and electrolyte replacement, which adds to maintenance costs. This study evaluates and demonstrates the capabilities of Fe-Ni batteries for participating in grid energy storage applications. Stable performance was observed frequency regulation (FR) testing at 100% and 50% state of charge (SOC)s, while at 50% SOC, there was a 14% increase in efficiency compared to 100% SOC. Although 25% SOC achieved higher efficiency, limited cyclability was observed due to reaching the discharge cutoff voltage. Optimal SOC selection, battery monitoring, maintenance, and appropriate charging strategies of Fe-Ni batteries seem to be crucial for their FR applications. Fe-Ni batteries exhibit stable peak shaving (PS) results, indicating their suitability and reliability under various load conditions for PS testing. Extended cycling tests confirm their potential for long-term grid-scale energy storage, enhancing their appeal for PS and FR applications.

25 ENERGY STORAGE↗

Coupled Experimental–Theoretical Characterization of a Carbon Electrode in Vanadium Redox Flow Batteries using X-ray Absorption Spectroscopy

Vanadium redox flow batteries (VRFBs) have emerged as promising solutions for stationary grid energy storage due to their high efficiency, scalability, safety, near room-temperature operation conditions, and the ability to independently size power and energy capacities. The performance of VRFBs heavily relies on the redox couple reactions of V 2+ /V 3+ and VO 2+ /VO 2 + on carbon electrodes. Therefore, a thorough understanding of the surface functionality of carbon electrodes and their propensity for degradation during electrochemical cycles is crucial for designing VRFBs with extended lifespans. In this study, we present a coupled experimental–theoretical approach based on carbon K edge X-ray absorption spectroscopy (XAS) to characterize carbon electrodes prepared under different conditions and identify relevant functional groups that contribute to unique spectroscopic features. Atomic models were created to represent functional groups, such as hydroxyl, carboxyl, methyl, and aldehyde, bonded to carbon atoms in either sp 2 or sp 3 environments. The interactions between functionalized carbon and various solvated vanadium complexes were modeled using density functional theory. A library of carbon K-edge XAS spectra was generated for distinct carbon atoms in different functional groups, both before and after interacting with solvated vanadium complexes. Here we demonstrate how these simulated spectra can be used to deconvolve ex situ experimental spectra measured from carbon electrodes and to track changes in the electrode composition following immersion in different electrolytes or extended cycling within a functional VRFB. By doing so, we identify the active species present on the carbon electrodes, which play a crucial role in determining their electrochemical performance.

25 ENERGY STORAGE↗

Lithium-ion hopping weakens thermal stability of LiPF 6 carbonate electrolytes

Lithium hexafluorophosphate (LiPF 6 )-based carbonate electrolytes are widely used in commercial lithium-ion batteries (LIBs), but their thermal instability limits the cycle life and safety of LIBs at elevated temperatures. Few studies have yielded insight into the initial PF 6 — decomposition reaction that promotes thermal instability of LiPF6-based electrolytes. Here, we find that lithium-ion hopping assisted by the overall reorientational motion of propylene carbonate molecules facilitates PF 6 — decomposition at elevated temperatures in 1 M LiPF 6 /propylene carbonate electrolyte. Further, we demonstrate that urea additives, by preventing lithium-ion hopping, suppress the initial LiPF 6 decomposition reaction and enhance the thermal stability of the electrolyte. LIB cell tests with LiNi 0.6 Mn 0.2 Co 0.2 O 2 ||Li 4 Ti 5 O 12 show improved LIB performance at elevated temperatures with the thermally stabilized electrolyte. This study provides key insights into the design of thermally stable LiPF 6 -based carbonate electrolytes for improving the cycle life, calendar life, and safety of LIBs in elevated-temperature applications.

25 ENERGY STORAGE↗

An Overview of the Design and Optimized Operation of Vanadium Redox Flow Batteries for Durations in the Range of 4–24 Hours

An extensive review of modeling approaches used to simulate vanadium redox flow battery (VRFB) performance is conducted in this study. Material development is reviewed, and opportunities for additional development identified. Various crossover mechanisms for the vanadium species are reviewed, and their effects on its state of charge and its state of health assessed. A stack design focusing on flow fields and an electrode design tailored to various flow fields are reviewed. An operational strategy that takes these parameters into account is reviewed for various operating envelopes, chosen based on end user preference in terms of minimizing capital cost or operation and maintenance cost. This work provides a framework for the design and operation of a VRFB for various grid services.

25 ENERGY STORAGE↗

Methane liquefaction with an active magnetic regenerative refrigerator

This manuscript reports liquefaction of methane using an active magnetic regenerative refrigerator (AMRR). The AMRR used to cool from 285 K to 135 K has two identical regenerators fabricated with adjacent layers of four ferromagnetic refrigerants, each with sequentially lower Curie temperatures and lesser masses from hot to cold temperatures. The dual multilayer regenerators were assembled in opposition with a single cold region between them. For this set of experiments equal mass of helium gas was pumped through all layers of the regenerators during the two flow steps of the four-step AMR cycle. After successfully reaching 135 K, a compact condensing coil-fin tube heat exchanger (HEX) with a small storage vessel was mounted in the cold region of the dual regenerator assembly to be cooled during the hot-to-cold helium flow from alternatively demagnetized regenerators. The cold HEX was used to cool and liquefy a process stream of methane gas supplied at 295 K and different pressures in different runs. Further, by measuring time to liquefy a known volume of methane at three different pressures, cooling powers of the AMRR as a function of temperature were determined. The resultant data were compared to those predicted by the AMRR performance model. Conclusions from these experiments and suggestions for future work are presented.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Valve Regulated Lead Acid Battery Evaluation under Peak Shaving and Frequency Regulation Duty Cycles

This work highlights the performance metrics and the fundamental degradation mechanisms of lead-acid battery technology and maps these mechanisms to generic duty cycles for peak shaving and frequency regulation grid services. Four valve regulated lead acid batteries have been tested for two peak shaving cycles at different discharge rates and two frequency regulation duty cycles at different SOC ranges. Reference performance and pulse resistance tests are done periodically to evaluate battery degradation over the time. The results of the studies are expected to provide a valuable understanding of lead acid battery technology suitability for grid energy-storage applications.

25 ENERGY STORAGE↗

Long-Term Structural and Chemical Stability of Carbon Electrodes in Vanadium Redox Flow Battery

Predicting the performance decay in carbon electrodes is critical to maximizing the longevity of redox flow battery (RFB) systems. This study investigates the effect of long-term cycling (over 8000 cycles) on the structural and chemical evolution of carbon electrodes. We find that the microstructural aspects such as graphitic stacking order and interlayer spacing along with overall morphological construct remains largely unchanged even after the prolonged cycling process. Conversely, significant changes in surface chemistry such as evolution of functional groups and point defects are evident from our combined multimodal spectroscopic and computational analysis. The XPS and FTIR analysis reveals chemical absorption of chloride counter anions at point defects within graphitic surface. Additionally, our results suggest that vanadium cation plays an important role in counter anion-carbon surface interaction and subsequently the surface chemistry evolutions. Our findings provide insights about surface chemical evolution that is critical for predicting electrode performance and longevity of RFB.

Modachur Sivakumar, Bhuvaneswari↗

Evaluating ZEBRA Battery Module under the Peak-Shaving Duty Cycles

With the recent rapid increase in demand for reliable, long-cycle life, and safe battery technologies for large-scale energy-storage applications, a battery module based on ZEBRA battery chemistry is extensively evaluated for its application in peak shaving duty cycles. First, this module is tested with a full capacity cycle consisting of a charging process (factory default) and a discharging process with a current of 40 A. The battery energy efficiency (discharge vs. charge) is about 90%, and the overall energy efficiency is 80.9%, which includes the auxiliary power used to run the battery management system electronics and self-heating to maintain the module operating temperature (265 °C). Generally, because of the increased self-heating during the holding times that exist for the peak shaving duty cycles, the overall module efficiency decreases slightly for the peak-shaving duty cycles (70.7–71.8%) compared to the full-capacity duty cycle. With a 6 h, peak-shaving duty cycle, the overall energy efficiency increases from 71.8% for 7.5 kWh energy utilization to 74.1% for 8.5 kWh. We conducted long-term cycling tests of the module at a 6 h, peak-shaving duty cycle with 7.5 kWh energy utilization, and the module exhibited a capacity degradation rate of 0.0046%/cycle over 150 cycles (>150 days).

25 ENERGY STORAGE↗

High-Pressure Apparatus for Monitoring Solid–Liquid Phase Transitions

This work presents a new technique for observing the solid–liquid phase transformations in complex diesel fuel blends and diesel surrogates under high-pressure conditions intended to simulate those occurring in vehicle fuel injectors. A high-pressure apparatus based on a visual identification of freezing and thawing has been designed and built to monitor phase behavior and determine the crystallization temperature of complex fuels to predict wax precipitation. The proposed methodology was validated using pure substances—n-hexadecane (C16H34), cyclohexane (C6H12), and a binary cyclohexane/n-hexadecane mixture—all of which have been well-characterized previously. The crystallization temperatures of these compounds were measured from atmospheric pressure to 400 MPa for temperatures varying from 290 to 363 K and compared to those reported in the literature. The standard error of the estimated temperatures, based on a given pressure, between the experimental data obtained in this work was compared to data in the literature from Domanska et al. This methodology is being extended to investigate the properties of more complex fuel mixtures.

High-Pressure, phase change, diesel, solidificatio↗

Highly Efficient Magnetocaloric Natural Gas Liquefaction (Final Report)

Over the twelve-month project the following achievements were accomplished: • Liquefication of methane as primary component of natural gas was accomplished with a magnetocaloric liquefier (MCL) prototype. This was the first time an MCL was used to liquefy methane. • Improved MCL designs were completed. • Cooling to 135 K from room temperature was achieved for the first time in a single MCL stage with dual, reciprocating four-layer regenerators. • Techno-economic analysis for a multi-stage 5 tonne/day magnetocaloric liquefier was completed. The detailed thermodynamic analysis of this MCL design showed a figure of merit (FOM) of 0.6 was achievable. This is a ~2x improvement over current state of the art. • Cost of an efficient 5 tonne/day LNG multi-stage liquefier was projected to be ~$\$$3.1 MM for the 5 tonne/day MCL with achievable design assumptions. • Market study of U.S. merchant LNG demand by energy sector was completed showing that at beginning of 2019, total use was ~2.5 million gallons/day primarily in three sectors that was filled by ~20 small companies in the merchant LNG supply business producing ~2.3 million gpd. These data exclude LNG produced at dedicated peak shaving and large export plants. • Business case for MCL technology based on LNG market study was completed showing the high FOM feature of MCL reduces cost of plant power, and lower capital cost reduces debt repayment and plant depreciation operating expenses. However, today’s demand for U.S. merchant LNG in most sectors is satisfied with conventional technology. Further, with today’s extremely low natural gas (NG) feedstock costs (e.g., ~$\$$1.8/MMBtu), the cost of fuel for NG gensets and for LNG feedstock is already very low. Therefore, possible new merchant LNG liquefier plant developers anticipating demand growth in the transportation, industrial, and electricity generation sectors do not obtain sufficient cost benefits to adopt new, commercially unproven MCL technology. • Other market factors such as remoteness from existing NG pipelines, or unfilled or unsatisfied applications such as boil-off gas re-liquefaction in LNG vessels, or policy factors such as some form of emissions-related fees may make lower capital costs and higher FOM of MCL technology attractive for new small-scale (~50 tonne/day) LNG plants. Two potentially attractive niche markets for MCL technology were identified: i) re-liquefaction of boil-off gas from large LNG transport vessels where severe transport conditions are problematic for conventional technology; and ii) providing LNG in distributed-scale plants that eliminate road transport costs to meet diverse, smaller-scale, distributed LNG bunkering fuel demands. By eliminating significant cryogenic tanker delivery costs and create an attractive cost-savings benefit with small-scale MCL plants.

03 NATURAL GAS↗

Active magnetic regenerative liquefier using process gas pre-cooling from bypass flow of heat transfer fluid

A process for liquefying a process gas that includes: introducing a heat transfer fluid into an active magnetic regenerative refrigerator apparatus that includes a low magnetic or demagnetized field section; continuously diverting a bypass portion of the heat transfer fluid from a cold side of the low magnetic or demagnetized field section into a bypass flow heat exchanger at a first cold inlet temperature; and continuously introducing the process gas into the bypass flow heat exchanger at a first hot inlet temperature and discharging the process gas or liquid from the bypass flow heat exchanger at a first cold exit temperature; wherein the temperature difference between bypass heat transfer first cold inlet temperature and the process gas first cold exit temperature is 1 to 5 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and Scale-up of Continuous Electrocatalytic Hydrogenation of Functionalized Nitro arenes, Nitriles and Unsaturated Aldehydes

Electrolysis reactors based on the filter-press architecture of redox flow batteries have proven to be effective and scalable towards the production of commercially relevant, pharmaceutical quantities of anilines (>500 kg/year) from halogen-, hydroxyl-, and carbonyl-substituted nitroarenes. Turbulent flow through the carbon felts on which the catalysts were supported facilitated scaling towards production levels because it conferred on the reactors scale-independent, plug flow-like residence time distributions and high mass transfer coefficients. Equipping the cells with micro-reference electrodes made it possible to transfer reaction conditions first developed in batch systems to the continuous flow reactors. The catalysts prepared by incipient wetness impregnation of metal salts into lightly oxidized carbon felt supports were readily generalizable.

Egbert, Jonathan D.↗

High performance redox flow battery stack

A redox flow battery stack cell frame comprising a support frame and a monolithic bipolar plate integrated within the support frame is disclosed. The bipolar plate comprises a plurality of interdigitated flow channels on at least one surface. The support frame comprises an inlet manifold formed into a facing surface of the first side of the frame, the inlet manifold comprising fluid inlet distribution channels in a serpentine arrangement, each fluid inlet distribution channel aligned with a single inlet flow channel of the bipolar plate; and an outlet manifold formed into the facing surface of the opposing side of the frame, the outlet manifold comprising fluid outlet distribution channels in a serpentine arrangement, each fluid outlet distribution channel aligned with a single outlet flow channel of the bipolar plate. Redox flow battery stack cells and stacks comprising the stack cell frame are also disclosed.

25 ENERGY STORAGE↗