Quantitative Life Prediction Using High Precision Coulometry with Automotive Current Rates

Know when to fold ‘em: An empirical description of risk management in public research funding

Simultaneous Pursuit of Discovery and Invention in the US Department of Energy

A framework for a hydrogen economy

This paper describes concepts to minimize the plume generated by unwanted sediments collected along with manganese nodules during hydraulic mining operations. The concept consists of two novel technologies: separating all sediment from the collected nodule slurry to eliminate sediment from entering the riser and lift system, thereby reducing, or eliminating a midwater plume, and subsea electrocoagulation (EC) to create rapidly settling flocs of sediment being discharged from the seafloor collector. The first approach involves designing a gravity separator (hopper) whereby the larger particles fall through an outlet and are entrained with clean water before entering the riser, while all the sediment and water collected with the nodules exits at the hopper overflow. To prevent sediment from being entrained with the nodules, a "reverse hydrocyclone" and secondary hopper is incorporated in the underflow circuit to help maintain a positive pressure differential between the riser inlet and the hopper during operations. The second approach employs the marinization of proven wastewater treatment EC technology to create large metalliferous flocs which attract the sediment causing rapid settling when the slurry is discharged aft of the collector. Work reported here includes numerical (CFD) confirmation of the separator performance, and experimental demonstration of the EC application, as well as techno-economic assessments of the cost impacts of implementing these technologies. This work was supported by the U.S. Department of Energy, Advanced Research Projects Agency – Energy (ARPA-E), and with contributions of sediment for the EC tests by The Metals Company from the Clarion Clipperton Zone and Ocean Minerals, LLC from the Cook Islands EEZ.

Distributed Energy Resources (DER) have increased penetration into the electric grid in recent years due to the growth of many renewable energy technologies as well as more efficient small conventional generation sources. Microgrids have grown in popularity along with the increased usage of DERs as a way to manage the multiple DERs on a local level.1Microgrids contain energy storage devices to store and distribute the intermittent energy provided by DERs (see figure 1).Coupling a solar energy resource with a Li-ion battery energy storage, we study the autonomy (the percentage of time the system meets demand) and utilization (amount of capacity used) during yearly operation.2By including a demand schedule with the coupled solar and battery system, we study both how different demands, system sizes and solar insolation patterns will affect the autonomy and utilization of the system. Both islanded and grid-tied demand structures will be discussed.The battery model involved in this study is an electrochemical and transport based Li-ion battery model.3For the solar portion of the model we will assess both ideal insolation curves as well as site based insolation data. For the real-site data, several solar monitoring sites within the US will be employed. The real data will offer a contrasting look at how much the coupled system can be affected on a daily and seasonal basis. In addition, using real data will allow for a greater assessment about the stability of a coupled system in areas with strong insolation, but high variability against areas of weaker insolation, but low variability. A balance between a high level of both autonomy and utilization will be studied in conjunction with preferable demand structures. This balance will affect the structure and operation of a microgrid with both solar and battery systems. Acknowledgements The authors acknowledge financial support from the U.S. Department of Energy’s Advanced Research Projects Agency- Energy (ARPA-E), and the Solar Energy Research Institute in India and the United States (SERIIUS), as well as, Washington University in St. Louis’ McDonnell Academy Global Energy and Environmental Partnership (MAGEEP).

Battery Management Systems (BMS) are critical to safe and efficient operation of lithium-ion batteries and accurate prediction of the internal states [1]. Smarter BMS that can estimate and implement optimal charging profiles in real-time are important for advancement of the Li-ion battery technology. Estimating optimal profiles using physics-based models is computationally expensive because of the non-linear and stiff nature of the model equations, involving the need for constrained non-linear optimization [2-12]. In this work, we present an alternative approach to control batteries applying the concept of differential geometry. This approach is known as Generic Model Control (GMC), or Reference System Synthesis [13,14]. This work enables robust stabilization and control of battery models to set-point as an alternative approach, eliminating the need to perform optimization of nonlinear models. This work builds on our previous work of implementation of GMC for differential variables occurring in a model consisting of differential algebraic equations (DAEs), and extends it to set point based control for algebraic variables. Conventional GMC is applicable for cases in which the output is typically independent of control [13]. We also extend it for cases for which the measured variable can be an explicit function of the manipulated variable. As compared to the generic model control approaches implemented by previous researchers, we have implemented the same concept using direct DAE numerical solvers [15]. The results are presented for single input single objective, and for constrained problems. The proposed approach is compared with standard control approaches and is found to be equally robust if not better. Acknowledgements The work presented herein was funded in part by the Advanced Research Projects Agency – Energy (ARPA-E), U.S. Department of Energy, under Award Number DE-AR0000275 and the Clean Energy Institute at the University of Washington, Seattle.

Liquid electrolyte solutions containing dissolved active material imbue Redox Flow Batteries (RFBs) with many unique benefits relative to solid-state electrochemical energy storage devices: long shelf-life, long system life-time, de-coupled rated energy and power, ease of recyclability.1 Operating a RFB system with flowing electrolyte solutions presents unique concerns as well, with one notable concern arising from possible precipitation of electrolyte. Precipitation of active material can have many consequences including sensor inaccuracy, inaccessible storage capacity, partially- or fully-blocked reactor electrode regions, and system clogging.Aqueous vanadium RFBs, a leading chemistry in commercial systems, has a precipitation mechanism at high temperatures for battery solutions containing commercially relevant vanadium concentrations >1.5 M. At elevated temperatures (> 40°C), positive electrolyte solutions can precipitate V2O5 dimers, first as a gel-like substance and eventually as solid particles.2 The UTRC team has developed recovery procedures for systems that may succumb to such precipitation events; in the case for aqueous vanadium RFBs, exposure of precipitate to lower oxidation state forms of vanadium (i.e. negative electrolyte) reduces and redissolves precipitated V2O5. This electrolyte takeover process (ETP) can successfully redissolve precipitates and recover performance from precipitate-induced cell/stack under-performance.As UTRC pursues alternative flow chemistries, the same ETP principles are applied to other chemistries such as polysulfide-based systems, known for sulfur crossover and precipitation of elemental sulfur in positive electrode volumes.3 This abstract will discuss the progress made at UTRC to recover from precipitation events in such chemistries, which, unlike aqueous vanadium, do not permit simple mixing of negative and positive electrolytes. Acknowledgements: The authors gratefully acknowledge support from Vionx Energy Corporation. Some of the work to be presented here was funded by the Advanced Research Projects Agency - Energy (ARPA-E), U.S. Department of Energy (DOE) under Award Number DE-AR0000994.

Metal-supported solid oxide fuel cells (MS-SOFC) offer the advantages of low-cost structural materials (e.g. stainless steel), mechanical ruggedness, excellent tolerance to redox cycling, and extremely fast start-up capability. Because of rapid-start capability, MS-SOFCs may be well-suited for portable, ruggedized, fast-start, intermittent-fuel, transportation, or other unique and innovative applications. The LBNL approach focuses on symmetric-architectured, co-sintered, ScSZ-based MS-SOFCs with porous metal supports on both anode and cathode sides, and catalysts deposited into both electrodes via infiltration (Fig 1). These features provide for a mechanically rugged cell that can be processed with low-cost scalable techniques, and for high surface-area catalysts that are deposited after sintering, thereby avoiding interdiffusion or coarsening during cell sintering.LBNL’s previous work on MS-SOFCs includes demonstration of A) Over 1000h operation in both hydrogen fuel cell and steam electrolysis modes [1,2], B) stable operation with direct internal reforming of ethanol-water blend fuel [3], C) startup within 10 sec for a bare cell and more than 200 rapid thermal cycles for a cell mounted on a test rig manifold [1,4], D) dynamic load-following with operating temperature fluctuating rapidly under load [5], and E) tolerance to multiple deep redox cycles [1].Previous demonstrations were achieved with button cells in the range 3 to 7 cm2 total cell area. In this work, the MS-SOFC cell area is scaled up to 50 cm2 and higher, Fig 2. Scale-up of the stainless steel and zirconia cell architecture is straightforward. The cell structure is prepared by tapecasting large sheets and laser cutting to size, which is amenable to making any size or shape cell. Due to the symmetric nature of the cell architecture, the large cells remain flat after sintering.Uniform catalyst deposition over a large area is, however, challenging. A number of improvements to the infiltration technique were developed, including: pre-oxidation of the stainless steel to enhance wetting of the aqueous catalyst precursor solution into the porous cell surface; development of highly concentrated Pr-oxide and Ni/doped-ceria precursor solutions that are shelf stable and low-viscosity; and, aerosol spray deposition of those solutions to uniformly coat the entire cell. With the improved infiltration, nearly identical performance for button and large cells is achieved. Spray deposition of shelf-stable aqueous solutions is also anticipated to be much more relevant to industrial-scale cell manufacturing, relative to LBNL’s previous molten salt infiltration technique.AcknowledgementsThe information, data, or work presented herein was funded in part by the Advanced Research Projects Agency – Energy (ARPA-E), U.S. Department of Energy under work authorization numbers 13/CJ000/04/03 and 18/CJ000/04/01. Funding for this work was provided by LBNL and the U.S. Department of Energy Advanced Manufacturing Office through a Technology Commercialization Fund grant number TCF-18-15740. This work was funded in part by the U.S. Department of Energy under contract no. DE-AC02-05CH11231.References Tucker, M.C., J. Power Sources 369 (2017) 6-12Shen, F., R. Wang, and M.C. Tucker, in preparationDogdibegovic, E., Y. Fukuyama, M.C.Tucker, Journal of Power Sources, 449 (2020) 227598Tucker, M.C., and A.S. Ying, International Journal of Hydrogen Energy, 38 (2017) 24426-24434Tucker, M.C., J. Power Sources, 395 (2018) 314-317 Figure 1

Rechargeable lithium-ion batteries have been extensively used in mobile communication and portable instruments due to their high volumetric and gravimetric energy density and low self-discharge rate, leading many scientists and engineers to work towards developing lithium-ion batteries with improved performance and longer life.In normal operation, an active solid-electrolyte-interface (SEI) layer forms in the first cycle of charging, due to reactions of lithium and solvent at the active surface (1,2). The SEI layer provides a barrier between the electrolyte and electrode to prevent further reaction while allowing lithium ions to permeate through the SEI layer in order to intercalate into and out of the bulk solid to store and release energy. However, the SEI layer continues to grow under repeated cycling. This growth increases the diffusion resistance of the lithium ions to the bulk active material, and removes cyclable lithium from the system, reducing the efficiency of the battery (1,2). This increased resistance can produce high temperature and can result in thermal runaway (3-5) within the battery. The properties and chemical composition of the SEI layer (active and passive) has been a subject of intense research due to its importance in the safety, capacity fade, and cycle life of Li-ion secondary batteries (6-12). Examination of the growth of the SEI layer as a mechanism for capacity fade has been performed using Kinetic Monte Carlo (KMC) simulations (13). This has provided valuable insight into the growth of the SEI layer and has shown the effects of high rates of charging on SEI layer passivation. These KMC simulations can be used to study the surface heterogeneity of the electrode surface as the passive layer is formed.The KMC model used will be expanded to a 2+1D model which tracks the thickness of the SEI layer over a representative surface of the solid particle. This will give a sense of the heterogeneity that arises in the SEI layer and will be coupled with the pseudo 2D model to simulate full battery operation. The P2D model will be converted from a system of partial differential equations to a system of ordinary differential equations by using reformulation techniques developed for the continuum model (14). The KMC model studies the events that occur in the SEI layer and the particle surface. For example, diffusion of the solvent in the SEI layer is modeled using the KMC approach. The reactions at the active material surface are modeled by considering the relative rate constants and using a random number generator to determine the event which occurs. In contrast, the continuum P2D model explains what happens in the bulk phases, and is deterministic. This coupled model will perform continuum calculations simultaneously with the KMC calculations. As passivation is considered in the KMC model, the capacity of the battery will fade with time, allowing for life time studies to be performed. This will lead to better understanding of the conditions which lead to capacity fade and better operation of lithium-ion batteries. Acknowledgements The authors acknowledge financial support by the National Science Foundation under grant numbers CBET-0828002, CBET-0828123, and CBET-1008692, and the Advanced Research Projects Agency – Energy (ARPA-E), U.S. Department of Energy, under Award Number DE-AR0000275.

Vibration fatigue of film cooling hole structure of Ni-based single crystal turbine blade: Failure behavior and life prediction

Large fixed and floating wind farms are planned in the US, the first of which will come on stream along the East Coast, and then possibly followed by the West Coast in deepwater. However, there are other regions in North and South America, and even the Caribbean that are rapidly aiming for offshore wind farms. One of those locations, offshore Texas, may develop ahead of the West Coast by taking advantage of the unparalleled expertise in ocean engineering in Texas gained through over 40 years of offshore oil and gas developments. In addition, Texas has regional competitive advantages that could result in another offshore boom for the region. Texas is the leading state for onshore wind power and consequently has some highly innovative research institutions and initiatives that could further push Texas to the forefront of regional, if not global, offshore wind technology development and deployment. The additional advantages that Texas can provide to wind farm developers based on its proximity to the Caribbean and South American offshore wind markets are also presented. As an example of innovation in Texas, the University of Texas at Dallas, DOE ARPA-E (Department of Energy Advanced Research Projects Agency – Energy) funded vertical axis wind turbine (VAWT) development is summarized (ARPA-E, 2020). While elements of VAWT technology are transferable to horizontal axis wind turbine (HAWT) technology to improve HAWT performance, more generally, the deployment of VAWTs overcomes many logistical and performance problems inherent in deploying HAWTs offshore. Such VAWT advantages are discussed. Two cases are presented comparing HAWT versus VAWT floating wind farms. The technology and execution differences of the two cases are compared and the net present value and internal rate of return are calculated conserving the technology differences. Discussion of forthcoming additional financing opportunities is also presented to illustrate how even in low-cost electric rate markets, offshore wind can still be feasible.

A US programme designed to support “high risk, high payoff” research into energy has handed out its first $150m in cash. The Advanced Research Projects Agency-Energy (ARPA-E) has funded 37 projects covering a range of topics in renewable energy. Run by the US Department of Energy (DOE), ARPA-E seeks to reduce greenhousegas emissions and lower US dependence on foreign sources of energy.

FuelCell Energy wins ARPA-E contract to develop SOFC energy storage solution

Scientists have complained that a new research body run by the US Department of Energy (DOE) is suffering from management problems and is rejecting funding proposals without stating why. The DOE's Advanced Research Projects Agency-Energy (ARPA-E) – created in 2007 – is designed to fund high-risk, high-payoff research and development projects in energy. However, the agency, which received its first budget in April, has so far turned down almost 95% of proposals after the first round.

Direct liquid fuel cells (DLFC) are attractive alternatives of batteries and hydrogen fuel cells for applications where high energy density and easy to refill are critical. For example, in powering a 200W-1kWh drone, a DLFC system can weigh only 1/10 of a battery and refill is simpler than hydrogen and faster than battery recharging. Among liquid fuels, ethanol stands out for its high energy density and ammonia is carbon free. A drawback is the lack of anode catalysts for complete oxidation of ethanol and ammonia at low potentials with sufficient activity per mass of platinum group metals (PGM). Dr. Shimshon Gottesfeld is currently leading an ARPA-E project on “Direct ammonia hydroxide exchange membrane fuel cells”, and I am in the team to develop high performance catalysts for ammonia oxidation reaction (AOR) with low PGM contents. While I learned from reading his papers on a wide range of topics and talking with him at conferences in many years, working under his leadership made me further appreciate his contribution in advancing fuel cell technologies. Inspired by his sharp and open mind in choosing and solving technical issues and in pursuing deep fundamental understandings, I’d like to discuss the challenges in developing anode catalysts for ethanol and ammonia oxidation and to illustrate promising directions and opportunities based on new insights in reaction mechanisms and material/structure/performance correlations. The performances of ethanol oxidation reaction (EOR) and AOR in alkaline media on the best catalysts that we recently developed will be presented and compared. The results show that facile EOR is possible at ambient temperature when a direct 12-electron EOR pathway is activated. Analyses of in situ infrared reflection absorption spectra indicate that the C-C bond splits via ethanol dissociation and full oxidation completes without CO as poisoning intermediate. However, carbonate formation in alkaline media lowers pH and reduces EOR activity. Carbon-free ammonia circumvents this issue, but AOR activity needs enhancement from elevated temperature due to the high activation barrier for N-N bond formation. Most studies so far focused on Pt-based catalysts and the polarization curves were measured at ambient temperature. Our study of temperature-dependent AOR kinetics found that activity enhancement from 25 to 60 oC is in the order of Ir (5.5) > IrPt (4.2) > Pt (2.0).1 For both EOR and AOR, Ir is effective in promoting dehydrogenation, and thus, in lowering the onset potentials. Thus, Ir-based catalysts are more promising than Pt-based catalysts for AOR. I’ll also show that the C-C bond cleavage in EOR and the N-N bond formation in AOR prefer distinctly different atomic structures. The new insights point out opportunities and directions for future studies. Acknowledgements The author thanks Zhixiu Liang, Liang Song, Jingyi Chen, Shiqing Deng, and Eli Stavitski for their collaborations. The work was funded by the Advanced Research Projects Agency-Energy (ARPA-E), U.S. Department of Energy, under Award Number DE-AR0000805 and by the Division of Chemical Sciences, Geosciences and Biosciences Division, US Department of Energy under contract DE-SC0012704. References Song, L. et al. Temperature-Dependent Kinetics and Reaction Mechanism of Ammonia Oxidation on Pt, Ir, and PtIr Alloy Catalysts. J. Electrochem. Soc. 165, J3095–J3100 (2018).