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DOE OSTI2018

Final Report for Project "A high-throughput pipeline for mapping inter-species interactions and metabolic synergy relevant to next-generation biofuel production"

The goal of our project was to implement a pipeline for the systematic, computationally-driven study and optimization of microbial interactions and their effect on lignocellulose degradation and biofuel production. We specifically sought to design and construct artificial microbial consortia that could collectively degrade lignocellulose from plant biomass, and produce precursors of energy-rich biofuels. This project fits into the bigger picture goal of helping identify a sustainable strategy for the production of energy-rich biofuels that would satisfy the existing energy constraints and demand of our society. Based on the observation that complex natural microbial communities tend to be metabolically efficient and ecologically robust, we pursued the study of a microbial system in which the desired engineering function is achieved through division of labor across multiple microbial species. Our approach was aimed at bypassing the complexity of natural communities by establishing a rational approach to design small synthetic microbial consortia. Towards this goal, we combined multiple approaches, including computer modeling of ecosystem-level microbial metabolism, mass spectrometry of metabolites, genetic engineering, and experimental evolution. The microbial production of biofuels from lignocellulose is a complex, multi-step process. Microbial consortia are an ideal approach to consolidated bioprocessing: a community of microorganisms performs a wide variety of functions more efficiently and is more resilient to environmental perturbations than a microbial monoculture. Each organism we chose for this project addresses a specific challenge: lignin degradation (Pseudomonas putida); (hemi)cellulose degradation (Cellulomonas fimi); lignin degradation product demethoxylation (Methylobacterium spp); generation of biofuel lipid precursors (Yarrowia lipolytica). These organisms are genetically tractable, aerobic, and have been used in biotechnological applications. Throughout the project, we have used mass spectrometry to characterize and measure the metabolic inputs and outputs of each of these consortium members, providing valuable information for model refinement, and enabling the establishment of metabolism-mediated interactions. In addition to lignocellulose degradation, we have started addressing the challenge of removing metabolites (e.g. formaldehyde) produced by the demethoxylation of lignin monomers, which can otherwise inhibit microbial growth due to their toxicity. On the computational side, we have implemented genome-scale models for all consortium members, based on KBase reconstructions and literature curation, and we studied small consortia and their properties. Overall, our project has identified a complex landscape of interactions types and metabolic processes relevant to community-level functions, illustrating the challenges and opportunities of microbial community engineering for the transformation of biomass into bioproducts.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Using Membranes with Internal Microchannels to Prevent Drying-out during CO 2 Electrolysis

Scaling up CO 2 electrolysis is a vital aspect in the transition to manufacturing sustainable fuels and chemical compounds, satisfying the demand for chemicals and demand for storing renewable electricity. Depending on the employed catalyst, different products can be produced, such as carbon monoxide and ethylene, by applying a voltage on a CO 2 and H 2 O fed electrolyzer. CO is a desirable product according to techno-economic analysis, because it can be produced selectively using a silver catalyst and is a precursor for hydrocarbons in the Fischer–Tropsch process. In a state-of-the-art CO 2 electrolyzer, two electrodes are directly pressed against an ion-exchange membrane – this is called a zero-gap configuration. Therefore, the membrane is a crucial component for the system, since it has the role of providing a conductive medium between the electrodes. One of the challenges in CO 2 electrolysis is that water is consumed in the reaction. At high current density, this may cause the membrane's surface near the cathode to dry out, lowering efficiency or perhaps stopping the process entirely, since there is no longer a conductive medium. As a result, water management is critical for this process. In this work, we approach the drying-out challenge by studying the novel concept of a membrane with internal microchannels. These channels allow the circulation of water or an electrolyte inside the membrane, which reduces the water diffusion path and affects the membrane’s conductivity. The effects of channel geometry, location, and concentrations of electrolyte inside on water content, conductivity and overall performance are studied in a 2D COMSOL model. In addition, the effect of internal concentration of electrolyte on the membrane’s resistance, on the process performance and the K + cross-over to cathode side were investigated experimentally. Our modeling results prove that the presence of the channels can keep the membrane hydrated. The highest current densities are observed when the channel is closest to the cathode, and with smaller pores. Smaller pores are advantageous due to the trade-off between enhanced membrane conductivity and the lower conductivity of the liquid itself. If water is circulated in a large channel, it increases the membrane’s ionomer conductivity due to hydration but the overall conductivity is decreased since water is not highly conductive. Nonetheless, the results also show that a higher concentration of electrolyte inside the microchannels can significantly increase the total conductivity of the membrane, and therefore the energy efficiency of the process. These effects are most significant at higher current densities. In the experimental results, we’ve observed similar effects in terms of membrane conductivity and current density of the process – the higher the electrolyte concentration the higher the current density. Furthermore, a low concentration decreases the amount of potassium which crosses over to the cathode side, inhibiting salt deposition. We’ve concluded that a small channel, up to 90 µm wide, close to the pore with an electrolyte with a concentration of up to 10 mM could be very beneficial for the water management and energy efficiency of the process. This helps to keep the membrane hydrated at higher current densities, improves the conductivity of the membrane, and it doesn’t have significant impacts on the salt deposition.

Petrov, Kostadin Veselinov↗

NASA NTRS1972

Fatigue experience from tests carried out with forged beam and frame structures in the development of the Saab aircraft Viggen

A part of the lower side of the main wing at the joint of the main spar with the fuselage frame was investigated. This wing beam area was simulated by a test specimen consisting of a spar boom of AZ 74 forging (7075 aluminum alloy modified with 0.3 percent Ag) and a portion of a honeycomb sandwich panel attached to the boom flange with steel bolts. The cross section was reduced to half scale. However, the flange thickness, the panel height, and the bolt size were full scale. Further, left and right portions of the fuselage frame intended to carry over the bending moment of the main wing were tested. Each of these frame halves consisted of a forward and a rear forging (7079 aluminum alloy, overaged) connected by an outer and inner skin (Alclad 7075) creating a box beam. These test specimens were full scale and were constructed principally of ordinary aircraft components. The test load spectrum was common to both types of specimens with regard to percentage levels. It consisted of maneuver and gust loads, touchdown loads, and loads due to ground roughness. A load history of 200 hours of flight with 15,000 load cycles was punched on a tape. The loads were randomized in groups according to the flight-by-flight principle. The highest positive load level was 90 percent of limit load and the largest negative load was -27 percent. A total of 20 load levels were used. Both types of specimens were provided with strain gages and had a nominal stress of about 300 MN/sq m in some local areas. As a result of the tests, steps were taken to reduce the risk of fatigue damage in aircraft. Thus stress levels were lowered, radii were increased, and demands on surface finish were sharpened.

Larsson, S. E.↗

DOE OSTI2018

Stasis PCM Test Results

A phase change material product distributed by Stasis Group, designed to reduce the cooling energy requirements of multi-story commercial buildings, was tested in a side-by-side comparison at FLEXLAB® (LBNL, 2018), a calibrated test facility for low energy building technology solutions. The product was installed according to Stasis recommendations in the ceiling plenum of a 600 ft 2 cell representative of an office space, while an identical cell was operated in the same conditions, except for the night-time pre-cooling sequence and without the product, to gather baseline data. The cells were operated to replicate summer conditions of a candidate office building for retrofit. For the tests conducted at FLEXLAB, two Phase Change Material (PCM) compositions were tested, with the second product having an upgraded composition for thermal performance and upgraded packaging that was used to meet with fire safety requirements for a plenum application. Two rounds of tests were performed, which were designed to collect data for both core (designated as Round 1) and perimeter (Round 2) office space conditions. Following the analysis of the data collected during Round 1, the experimental design was modified to better represent the thermal conditions of a typical office space in relation to the PCM performance. A new product was also brought in for testing in Round 2, which had an improved operational temperature range and packaging properties. In Round 1, multiple tests were conducted to evaluate the performance of the product under different conditions of internal loads, temperature setpoints, pre-cooling strategies and temperature control strategies. In Round 2, the internal conditions were kept constant, while the test conditions only differ in the amount of PCM installed in the test cell plenum and the length of the nighttime pre-cooling sequence. The performance benefits of PCM are generally two-fold: the material may reduce peak cooling energy use during daytime hours (a peak demand energy use benefit) and may allow for energy savings with pre-cooling at night through night flush HVAC controls when night time outside air temperatures are lower, and fan energy use for cooling is more efficient than the use of daytime compressor-based cooling. The focus of this research project was mainly on quantifying the energy savings potential of the latter case although some effects on peak reduction were noted. Between the cell with PCM and nighttime precooling and the reference cell without PCM or precooling, a reduction in cooling load during occupied hours was noted between 7.6 kWh (or 22% of occupied hours cooling load) and 12.5 kWh (or 33% of occupied pg. 7 hours cooling load). Future work can further evaluate the peak cooling load reduction benefits of this product in more detail. This report highlights the results of Round 2, which reflect the performance of the modified PCM product when operated in suitable conditions. The results of Round 1, along with an analysis of the experimental data to identify the factors that prevented the product from performing as desired are presented in Appendix B.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2015

Nuclear-Renewable Energy Systems Secondary Product Market Analysis Study

In order to properly create a program surrounding the development of any technological concept it is necessary to fully understand the market in which it is being developed. In the case of Integrated Nuclear-Renewable Hybrid Energy Systems (HES), there are two economic markets in which it must be able to participate in: the electricity market and the secondary product market associated with the specific system. The purpose of the present report is to characterize the secondary product market in the U.S. and to provide recommendations for further developing the HES program. While HESs have been discussed in depth in many other reports, it is helpful to discuss them briefly in the present work [REF]. The concept of the HES can be deduced to a system, featuring a combination of a nuclear power plant, a renewable energy source, and an industrial manufacturing plant . The system is designed in a fashion that allows it either to produce electricity or to manufacture a secondary product as needed. The primary benefit of this concept lies in its ability to maximize economic performance of the integrated system and to manufacture products in a carbon-free manner. A secondary benefit is the enhanced supply-side flexibility gained by allowing the HES to economically provide grid services. A key tenant to nuclear power plant economics in today’s electricity market is their ability to operate at a very high capacity factor. Unfortunately, in regions with a high penetration of renewable energy, the carbon free energy produced by nuclear power may not be needed at all times. This forces the nuclear power plant to find a user for its excess capacity. This may include paying the electric grid to find a user, releasing energy to the environment by ‘dumping steam’, or reducing power. If the plant is unable to economically or safely do any of these actions, the plant is at risk of being shutdown. In order to allow for nuclear power plants to continue to contribute carbon free electricity to the grid in a future with high renewable energy penetration, HESs allow for excess capacity to be diverted to a chemical process. If the chemical products sold on the market replace those sold previously – which would be the case if a currently operating manufacturing plant was modified to be a HES component – then the products would now be produced with reduced emission of carbon and other greenhouse gases. There are several key economic barriers that must be surmounted for HESs to be developed. The two primary barriers are the increased capital cost associated with coupling and controlling the HES components and the decreased utilization of the manufacturing plant capital due to intermittent energy delivery . Because of this, manufacturing plants that are less complex and have smaller non-variable operations and capital costs may be more attractive for integration. A secondary economic barrier for the HES is the market availability for its products. The system must operate a region where there is either an intermittent demand for its electricity, an intermittent demand for its secondary product, or both. In a region with an intermittent demand, product prices should shift accordingly, making it less attractive to produce one of the products. The HES then can shift production in order to maximize profit. Without an intermittent demand for at least one of its products, there would be little need for it to expend the extra capital required for integration as an HES.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2021

DEVELOPMENT OF STABLE ANODE AND CATHODE MATERIALS FOR RECHARGEABLE BATTERIES

Batteries have been employed in a variety of applications, such as portable electronics, electric vehicles (EVs), and stationary energy storage to preserve energy from other renewable sources (like wind or solar energy). The ultimate goal is to develop high energy density, long life span, better safety, and low cost of the batteries. However, current commercialized batteries (like lead-acid, zinc-alkaline, lithium-ion batteries (LIBs)) could not fulfill all the demands of diversified applications. LIBs predominate the market because of their high energy density. To achieve a higher capacity of the cell, high-nickel layered (Ni > 90%) cathode materials are promising candidates since they compose high specific capacity and discharge voltage. In chapter 1, an introduction to cell energy density and the development of high-nickel layered cathode materials along with associated obstacles of poor cycling stability and thermal stability have been discussed. Associated works like doping or surface coating have also been mentioned in this section. In chapter 2, Al doping in high-nickel layered cathode materials to enhance the structural and thermal stability was introduced. Uniform incorporation of Al doping is achieved by mechanical fusion and calcination processes. The Al doping not only decreased the Li/Ni mixing ratio but also enhance the thermal resistance to oxygen evolution because of strong Al-O bonding, which leads to elevated electrochemical and thermal stability. In chapter 3, TiN is implemented as a Ti dopant for high-nickel layered cathode materials to improve the electrochemical performance in the LIBs. The Ti not only diffused within the bulk structure but also formed segregation on the surface, which improved the structural stability and led to better cycling performance. Although LIBs deliver high energy density, safety concerns of flammable organic electrolytes have not been resolved yet. Therefore, the aqueous rechargeable zinc-ion batteries (ZIB) have been praised for their safe, low-cost, eco-friendly stationary energy storage, which is considered as a complementary system to LIBs. In chapter 4, the mechanism, advantages, and challenges of ZIBs would be given and the strategies for solving the zinc metal anode issues have been discussed in this section. In chapter 5, a polymer coating method was reported to facilitate Zn deposition/ stripping by coordination with Zn2+ and prevented direct contact with aqueous electrolyte to block corrosion side-reactions. With this coating, a boost in a lifetime (up to 400 hours) and lower polarization under extremely high current conditions (10 mA cm-2) have been achieved in repeated Zn deposition/ stripping cycling.

25 ENERGY STORAGE↗

DOE OSTI2021

AGGREGATE: dAta-driven modelinG preservinG contRollable dEr for outaGe mAnagemenT and rEsiliency (Final Report)

The AGGREGATE project team successfully developed and validated various modules for outage management. Brief summaries of each module are provided to showcase their strength for outage management and restoration for a distribution system with a high penetration of connected distribution energy resources (DERs). In recent years, inverter-based DERs have been widely deployed in distribution system. A most of behind-the-meter (BTM) solar power generation is not visible to the utility. The data-driven DER and load estimation modules are using machine learning (ML) and artificial intelligence (AI) to manage this issue, which provides an opportunity for distribution system operators (DSOs) to operate systems and make decisions in real-time for a distribution system with a high penetration of DERs deployed. Also, the estimated DER and true load can be further leveraged in network aggregation and cold-load pick up estimation for reducing the computing complexity and providing for fast restoration. After load demand and DER power generations have been estimated, the information will support topology and state estimation (SE). The topology estimation module demonstrated the viability of mixed integer linear programming (MILP) formulation to estimate the most likely operational radial topology and outage sections using power flow measurements, historical/estimated load and DERs data and smart meter ping measurements. Formulation includes continuous (power flow, load and DERs data) and binary measurements (smart meter ping measurements) in a single formulation. Errors in continuous data and binary data are modeled as normal distribution and Bernoulli distribution, respectively. In the future distribution grid, the power injection from controllable DERs will be essential for efficient and resilient grid operation. However, determining the optimal DER injections and restoration actions is dependent on knowledge of the system states. State estimation (SE), already the cornerstone of transmission energy management systems, will become commonplace in distribution management systems as more measurements become available from deployment of automated metering infrastructure (AMI). Observability analysis is the first step in SE, as it determines the sufficiency of the available measurements for accurately estimating the current system states. A new type of pseudo-measurement called a Correlational Measurement (CM) is introduced in this module, to enhance the observability of the system to enable more accurate SE. CMs encapsulate knowledge of correlation between demand patterns for similar classes of loads as well as injection patterns for same-technology renewable DERs. During grid contingency scenarios, DERs have been traditionally disconnected, without any fault ride-through capabilities. However, with new regulations and better technology, it is feasible for these resources to contribute to the grid’s restoration after an adverse event and hence enhance resilience. The controllability module proposes a two-step restoration scheme for the power system restoration process by leveraging additional degrees of freedom in power electronics interfaced DERs for mitigating voltage problems. In a resilience mode without the utility system, the distribution grid relies on DERs to serve critical load. In such a severe event with multiple faults on the distribution feeders, actuation of various protective devices (PDs) divides the distribution system into electrical islands. The undetected actuated PDs due to fault current contributions from DERs can delay the restoration process, thereby reducing the system resilience. The Advanced Outage Management (AOM) and the Advanced Feeder Restoration (AFR) modules developed in this project provide improved system resilience with multiple DERs. AOM identifies the faulted sections and actuated PDs in a distribution system with DERs by incorporating smart meter data. The most credible outage scenario including fault locations, PD actuations, and fault indicator (FI) failures is identified by a set of binary integer linear programming incorporating hypotheses. The AFR module serves to restore a distribution system with available energy resources taking into consideration the availability of utility sources and DERs. By partitioning the system into islands, critical load will be served with the available generation resources within islands based on the solution of a MILP. When the utility systems become available, the optimal path will be determined by a spanning tree search algorithm that reconnects these islands back to substations and restores the remaining load. The transmission and distribution (T&D) co-simulation module was used to validate the effect of a control action performed on the distribution side assets as it propagates to the transmission side. This ensures that the control action performed results in a feasible operating point on both the transmission and the distribution system. In addition to validation, the team used the T&D co-simulation module to demonstrate how distribution system assets can be used to mitigate issues on the transmission system. Specifically, the team demonstrated that appropriate switching operations on the distribution side can alleviate the line overload condition on the transmission side without causing new operational constraint violations.

24 POWER TRANSMISSION AND DISTRIBUTION↗

DOE OSTI2024

High-Fidelity and High-Performance Computational Simulations for Rapid Design Optimization of Sulfur Thermal Energy Storage

Industrial process heating (IPH) accounts for approximately 70% of US manufacturing energy use and is primarily produced by fossil fuel combustion. Approximately 1500 TWht (approximately 60%) of IPH demand is in the temperature range of 100-300. Industrial applications in this temperature range include drying, hydrothermal processing, thermal enhanced oil recovery, food and beverage, bioethanol production, etc. Cost-effective thermal energy storage (TES) that increases the utilization of waste and renewable heat (solar, geothermal, etc.) could provide significant energy savings and reliable heat sources, decrease emissions, and increase US manufacturing competitiveness through reductions in fuel consumption. TES development has historically been dominated by technologies suitable for deployment with concentrating solar power (CSP). State-of-the-art thermal storage deployed commercially with power tower CSP plants uses a 60%/40% NaNO3/KNO3 molten salt and operates between temperatures of approximately 280 degrees Celsius and 570 degrees Celsius using a two-tank configuration. However, these nitrate salts are unsuitable for operation outside of this temperature range due to a high freezing point of approximately 220 degrees Celsius, and limits on high-temperature salt stability and corrosion resistance of containment alloys. Other materials being investigated for TES include those based on: (1) sensible energy storage (various molten salt compositions, inert solid particles, rocks or pebble beds, sulfur, water, concrete, graphite, etc.), (2) latent energy storage in materials that undergo solid-liquid phase change at relevant temperatures (organic materials for low-temperature applications, inorganic salts and/or metals for high-temperature applications), or (3) thermochemical energy storage (hydrides, hydroxides, carbonates, metal oxides, etc.). The application temperature and challenges pertaining to storage material and/or containment cost, energy density, long-term thermal and cyclic stability, and charge/discharge heat transfer effectiveness drive material selection for a given IPH or electricity generation application. Sulfur is a cheap commodity at $80/ton compared to $1100 - 1300/ton for conventional salts. When using a metric of storage cost per kWh, sulfur costs around 2-3 $/kWh. Previous sulfur TES development focused on high temperature (>600 degrees) concentrated solar power applications with sulfur encapsulated in pipes and flow of gaseous HTF (air) in the shell side. However, for lower-temperature IPH applications in the range of approximately 100-300 degrees Celsius Element 16 adopted a compact and scalable TES design with molten sulfur in the shell and HTF pipes submerged in the molten sulfur bath. The low-cost molten sulfur TES for dispatchable IPH has deployment potential for broad applications. The spatial and temporal evolution of the HTF and sulfur temperature is critical to the TES system performance, and thus detailed modeling can improve understanding of the performance and facilitate design improvements. Using high performance computing and computational fluid dynamics (CFD) a low-cost molten sulfur thermal energy storage (TES) system for industrial process heating (IPH) applications was developed. The unique challenges in CFD modeling of sulfur TES are the sharp property changes of sulfur relevant to the working temperatures. Above 159, liquid sulfur undergoes polymerization, and the viscosity of sulfur rapidly increases by several orders of magnitude between 159 degrees Celsius and 188 degrees Celsius, followed by a decrease in viscosity beyond 188 degrees Celsius due to thermal bound dissociation. In addition, various concentrations of H2S impurities can also modify sulfur viscosity. This numerical challenge is especially relevant to transient simulation of the sulfur TES charging and discharging processes as the extreme property variations limit the applicability of traditional heat transfer correlations. Transient CFD simulations including the temperature-dependent sulfur properties and geometric complexity of the TES design were used to predict the effect of natural convection during charging and discharging on the heat transfer process, sulfur temperature uniformity, charge/discharge rates, and performance of the storage devices. The CFD model was validated with experimental results for a full charge and discharge cycle. The work will show 3D and 2D simulation comparisons aimed to facilitate rapid design iterations and a machine learning based design optimization approach.

CFD↗

DOE OSTI2020

WIPP Safety Significant Confinement Ventilation System (SSCVS) HEPA Filtration System - 20165

Construction and major equipment fabrication are underway for a new ventilation exhaust system at the Waste Isolation Pilot Plant (WIPP). The new system will provide continuous High Efficiency Particulate Air (HEPA) filtration of the exhaust from the WIPP underground while meeting the ventilation demands for expanded waste emplacement and mining operations over the next 40 years. The integrated system design provides for reducing the salt, clay and diesel particulates from the exhaust airflow from the mine, prior to full filtration using Nuclear Safety Significant HEPA filters. The SSCVS design and equipment provides for continuous HEPA filtration over a wide range of operating and environmental conditions. The new exhaust system connects to the existing underground exhaust shaft, and the exhaust air flows from the underground through Salt Reduction Units (SRUs) to protect the final filter banks from excessive moisture and rapid salt/dust buildup. Each of the six (6) SRUs consists of a demister to remove entrained moisture, a dry salt remover unit to filter approximately 90% of the entrained salt/dust, and an automated water treatment system to periodically clean the demisters and to remove salt from the SRU filters. At the maximum expected exhaust flowrate of 540,000 Cubic Feet per Minute (CFM) / 255 Cubic Meters per Second (m{sup 3}/s), five (5) salt removal units will be in operation with one unit in standby or maintenance. An in-line variable frequency drive booster fan will offset pressure losses through each SRU and reduce the relative humidity of the air exiting the SRUs. In the event of a high radiation alarm from the underground Continuous Air Monitors (CAMs), the SRUs will be automatically bypassed, which places the SRS and building outside of the Safety Significant confinement boundary. From the SRUs, the exhaust is directed to the HEPA filter banks located in the New Filter Building. The exhaust system is designed to provide continuous HEPA filtration prior to release to the exhaust stack. There are 22 HEPA filter banks rated at 27,000 CFM / 12.75 m{sup 3}/s each. Each filter bank has two stages of pre-filters and two stages of HEPA filters. The filtered air from each of the 22 filter banks discharges into a common concrete plenum, which is maintained under a negative pressure by the main exhaust fans. Six 1,000 HP variable frequency drive exhaust fans are provided on the south side of the plenum. At the maximum expected exhaust flow of 540,000 CFM, four exhaust fans and twenty filter banks will be in operation. The fans discharge vertically to a separate concrete exhaust plenum. The filtered exhaust is routed from the exhaust plenum to a 125-foot-tall exhaust stack via a 13-foot diameter duct. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2019

Pathways for practical high-energy long-cycling lithium metal batteries

Lithium (Li)-ion batteries play a critical role in modern day technologies, but their specific energy (Wh kg-1) and energy density (Wh L-1) are approaching the maximum practically achievable values based on existing manufacturing processes with the conventional cathode and anode materials. Developing the next generation rechargeable batteries with a specific energy higher than 300 Wh kg-1, up to 500 Wh kg-1, is a significant challenge. This paper discusses the pathways to build the next generation 500 Wh kg-1 rechargeable Li battery based on Li metal anode and a high nickel-content lithium nickel-manganese-cobalt oxide (high-Ni NMC) cathode. The fundamental requirements and practical technical approaches will be explored to hopefully address this grand challenge. In particular, we discuss the detailed cell level requirements and parameters to achieve high energy density, as well as the significant scientific challenges and potential solutions, including but not limited to enable the direct utilization of Li metal anode with high efficiency and long-term cycling stability, dendrite-free Li metal deposition, high utilization of the cathode materials with high mass loading and reasonable electrode thickness along with minimum parasitic weight in the cathode side. The cell level understanding and validation of the materials properties for high performance and control of interfacial reactions across the whole cell will be explored. New concepts in emerging multifunctional materials and electrolytes/additives and their implications will also be discussed.

lithium metal anode, lithium nickel manganese coba↗

DOE OSTI2015

Nanostructured Electrolytes for Stable Lithium Electrodeposition in Secondary Batteries

Secondary batteries based on lithium are the most significant energy storage technology for contemporary portable devices. The lithium ion battery (LIB) in widespread commercial use today is a compromise technology. It compromises high energy, high power, and design flexibility for long cell operating lifetimes and safety. Materials science, transport phenomena, and electrochemistry in the electrodes and electrolyte that constitute such batteries are areas of active study worldwide because significant improvements in storage capacity and cell lifetime are required to meet new demands, including the electrification of transportation and for powering emerging autonomous aircraft and robotics technologies. By replacing the carbonaceous host material used as the anode in an LIB with metallic lithium, rechargeable lithium metal batteries (LMBs) with higher storage capacity and compatibility with low-cost, high-energy, unlithiated cathodes such as sulfur, manganese dioxide, carbon dioxide, and oxygen become possible. Large-scale, commercial deployment of LMBs are today limited by safety concerns associated with unstable electrodeposition and lithium dendrite formation during cell recharge. LMBs are also limited by low cell operating lifetimes due to parasitic chemical reactions between the electrode and electrolyte. These concerns are greater in rechargeable batteries that utilize other, more earth abundant metals such as sodium and to some extent even aluminum. Inspired by early theoretical works, various strategies have been proposed for alleviating dendrite proliferation in LMBs. A commonly held view among these early studies is that a high modulus, solid-state electrolyte that facilitates fast ion transport, is nonflammable, and presents a strong-enough physical barrier to dendrite growth is a requirement for any commercial LMB. Unfortunately, poor room-temperature ionic conductivity, challenging processing, and the high cost of ceramic electrolytes that meet the modulus and stability requirements have to date proven to be insurmountable obstacles to progress. In this Account, we first review recent advances in continuum theory for dendrite growth and proliferation during metal electrodeposition. We show that the range of options for designing electrolytes and separators that stabilize electrodeposition is now substantially broader than one might imagine from previous literature accounts. In particular, separators designed at the nanoscale to constrain ion transport on length scales below a theory-defined cutoff, and structured electrolytes in which a fraction of anions are permanently immobilized to nanoparticles, to a polymer network or ceramic membrane are considered particularly promising for their ability to stabilize electrodeposition of lithium metal without compromising ionic conductivity or room temperature battery operation. Furthermore, we review recent progress in designing surface passivation films for metallic lithium that facilitate fast deposition of lithium at the electrolyte/electrode interface and at the same time protect the lithium from parasitic side reactions with liquid electrolytes. An enticing finding from both theory and experiment is that simple film-forming halide salt additives in a conventional liquid electrolyte can substantially extend the lifetime and safety of LMBs.

25 ENERGY STORAGE↗

NASA NTRS2000

Bubble Formation on a Wall in Cross-Flowing Liquid and Surrounding Fluid Motion,With and Without Heating

Application of gas-liquid two-phase flow systems for space-based thermal management and for the HEDS program demands a precise control of bubble size distribution in liquid. The necessity of bulk liquid motion for controlling bubble size and frequency in the space environment has been suggested by recent studies on pool, forced convection boiling and bubble formation in flowing liquid. The present work, consisting of two parts, explores bubble generation at wall in a cross-flowing liquid, i.e., in a forced convection boiling configuration. A schematic is shown. The first part looks into the bubble formation process under isothermal conditions in a reduced gravity environment, by injecting gas through a hole in the wall of a flowing liquid channel. In the latter part with channel wall heating, flow and temperature fields near a single bubble are studied under normal (1-g) and micro-gravity (mu-g) conditions. The objective of the isothermal experiments is to experimentally investigate the effects of liquid cross-flow velocity, gas flow rate, and orifice diameter on bubble formation. Data were taken mainly under reduced gravity conditions but some data were taken in normal gravity for comparison. The reduced gravity experiment was conducted aboard the NASA DC-9 Reduced Gravity Aircraft. The results show that the process of bubble formation and detachment depends on gravity, the orifice diameter (D(sub N)), the gas flow rate (Q(sub g)), and the liquid cross-flow velocity (U(sub L)). The reduced gravity data are shown. The data are analyzed based on a force balance, and two different detachment mechanisms are identified. When the gas momentum is large, the bubble detaches from the injection orifice as the gas momentum overcomes the attaching effects of liquid drag and inertia. The surface tension force is much reduced because a large part of the bubble pinning edge at the orifice is lost as the bubble axis is tilted by the liquid flow. When the gas momentum is small, the force balance in the liquid flow direction is important, and the bubble detaches when the bubble axis inclination exceeds a certain angle. With wall heating, liquid motion around an air bubble in cross-flowing 2cs silicone oil is experimentally investigated in 1-g. A spectral element based steady 2D numerical model is also developed. The traces of particles from experimental flow visualization and the corresponding computed streamlines are shown. At the upstream side of the bubble facing the cross-flow, thermocapillary and forced convection create liquid motion away from the wall, up along the surface. At the downstream side, a competing interaction between the two creates a recirculation cell, causing the bulk liquid to stagnate on the surface and separate thereafter. The important dimensionless parameters are - Surface tension and local cross-flow Reynolds numbers R(sub sigma)(U(sub ref)a/v) and Re(sub loc)(U(sub L)a/v), respectively based on reference thermocapillary U(sub ref)(sigma(sub T)Delta.T/mu, Delta T=T(sub wall)-T(sub liquid)) and local cross-flow velocity U(sub L), Prandtl number P(sub r) and Grashoff number Gr(rho.g.beta.DeltaTa(sup 3)/mu.v). Variation of the stagnation point with R(sub sigma) and Re(sub loc) is shown. Also shown are good agreement between experimental and numerical results in 1-g. The computational model is extended to mu-g condition to investigate temperature and velocity on the bubble surface, stagnation and reattachment points of the recirculation cell and wall heat transfer. It is observed that wall heating significantly alters the flow field around the bubble and thus the forces acting on the bubble, which control its detachment. Thus a combination of heating and liquid cross-flow can be utilized to precisely control bubble formation in a mu-g environment.

Bhunia, Avijit↗

DOE OSTI2013

Phase II Nevada Water Resources Data, Modeling, and Visualization (DMV) Center (Final Report)

Water is unquestionably a critical resource throughout the United States. In the semi-arid west -- an area stressed by increase in human population and sprawl of the built environment -- water is the most important limiting resource. Crucially, science must understand factors that affect availability and distribution of water. To sustain growing consumptive demand, science needs to translate understanding into reliable and robust predictions of availability under weather conditions that could be average but might be extreme. These predictions are needed to support current and long-term planning. Similar to the role of weather forecast and climate prediction, water prediction over short and long temporal scales can contribute to resource strategy, governmental policy and municipal infrastructure decisions, which are arguably tied to the natural variability and unnatural change to climate. Change in seasonal and annual temperature, precipitation, snowmelt, and runoff affect the distribution of water over large temporal and spatial scales, which impact the risk of flooding and the groundwater recharge. Anthropogenic influences and impacts increase the complexity and urgency of the challenge. The goal of this project has been to develop a decision support framework of data acquisition, digital modeling, and 3D visualization. This integrated framework consists of tools for compiling, discovering and projecting our understanding of processes that control the availability and distribution of water. The framework is intended to support the analysis of the complex interactions between processes that affect water supply, from controlled availability to either scarcity or deluge. The developed framework enables DRI to promote excellence in water resource management, particularly within the Lake Tahoe basin. In principle, this framework could be replicated for other watersheds throughout the United States. Phase II of this project builds upon the research conducted during Phase I, in which the hydrologic framework was investigated and the development initiated. Phase II concentrates on practical implementation of the earlier work but emphasizes applications to the hydrology of the Lake Tahoe basin. Phase 1 efforts have been refined and extended by creating a toolset for geographic information systems (GIS) that is usable for disparate types of geospatial and geo-referenced data. The toolset is intended to serve multiple users for a variety of applications. The web portal for internet access to hydrologic and remotely sensed product data, prototyped in Phase I, has been significantly enhanced. The portal provides high performance access to LANDSAT-derived data using techniques developed during the course of the project. The portal is interactive, and supports the geo-referenced display of hydrologic information derived from remotely sensed data, such as various vegetative indices used to calculate water consumption. The platform can serve both internal and external constituencies using inter-operating infrastructure that spans both sides of the DRI firewall. The platform is intended grow its supported data assets and to serve as a template for replication to other geographic areas. An unanticipated development during the project was the use of ArcGIS software on a new computer system, called the IBM PureSytems, and the parallel use of the systems for faster, more efficient image processing. Additional data, independent of the portal, was collected within the Sagehen basin and provides detailed information regarding the processes that control hydrologic responses within mountain watersheds. The newly collected data include elevation, evapotranspiration, energy balance and remotely sensed snow-pack data. A Lake Tahoe basin hydrologic model has been developed, in part to help predict the hydrologic impacts of climate change. The model couples both the surface and subsurface hydrology, with the two components having been independently calibrated. Results from the coupled simulations involving both surface water and groundwater processes show that it is possible to fairly accurately simulate lake effects and water budget variables over a wide range of dry and wet cycles in the historical record. The Lake Tahoe basin is representative of the hydrology, topography and climate throughout the Sierra Nevada Range, and the entire model development is prototypical of the efforts required to replicate the decision support framework to other locales. The Lake Tahoe model in particular, could allow water managers to evaluate more accurately components of the water budget (ET, runoff, groundwater, etc) and to answer important questions regarding water resources in northern Nevada. This report discusses the geographic scale and the hydrologic complexity of the calibrated model developed as part of this project, as well as simulation results for historical and future climate projects To enable human-driven data exploration and discovery, de novo software for a globalized rendering module that extends the capability of our evolving custom visualization engine from Phase I (called SMEngine) has been developed. The new rendering component, called Horizon, supports terrain rendering capable of displaying and interrogating both remotely sensed and modeled data. The development of Horizon necessitated adaptation of the visualization engine to allow extensible integration of components such as the global rendering module and support for associated features. The resulting software is general in its GIS capability, but a specific Lake Tahoe visualization application suitable for immersive decision support in the DRIVE6 virtual reality facility has been developed. During the development, various features to enhance the value of the visualization experience were explored, including the use of hyperspectral image overlays. An over-arching goal of the visualization aspect of the project has been to develop and demonstrate the CAVE (CAVE Automatic Virtual Environment) as a practical tool for hydrologic research.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2018

High Ion-Accessible Surface Area CNT-Ultracapacitors for Groundwater Desalination

Fresh water is a vital resource for human survival, as well as a key component for a wide range of industrial and agricultural needs. However, only 0.65% of the world’s water resources are available as fresh water, and the demand on the world’s water reserves continues to rise, with the demand already beginning to outpace the supply in many areas. A water-energy nexus is being reached that requires low -cost and -energy solutions for various degrees of treated water. Public awareness of the problem has also risen, such that in a 2012 survey, 88% of Americans reported concerns about potential water shortages. Approximately two-thirds of the world’s population could suffer water shortages over the next few years. Seawater and other saline water supplies make up around 98% of the world’s accessible water. Properly treated to reduce the levels of salinity, this represents an almost unlimited supply of fresh water. The high energy requirements, capital costs, and maintenance requirements to remove salts and other unwanted compounds, however, are barriers to widespread implementation of salt-to-freshwater facilities. These facilities most commonly use reverse osmosis (RO) systems that suffer from high required pressures and failures of moving parts; additionally, these facilities consume much grid energy and require constant maintenance, leading to high capital and operational costs. The RO process also generates large volumes of highly concentrated bio-hazardous brine that is costly to safely return to the ocean. In contrast to RO, capacitive desalination or capacitive deionization (CDI) has fewer moving parts (a low-pressure pump and several valves), operates at low pressure, and does not generate large quantities of brine that are hazardous to marine life. The capacitive charge/discharge of a CDI system can be cycled almost indefinitely, and the system has low energy requirements because the capacitive discharge electrical current can be co-generated back to the system. RO must remove the water from the salt while CDI removes the salt from the water. This represents a significant difference in the number of molecules which must be moved and energy required to desalinate water. However, CDI has not seen widespread use for large- or small-scale desalination because electrode efficiency has limited the extraction rate below what is useful for most applications. Mainstream demonstrated the following successes during this SBIR program: Performance - We developed an innovative new electrode structure for the high-efficiency removal of ions from salt-contaminated water samples by CDI. Based on prototype electrochemical tests, our CDI consumes as low as 0.71 kW/m 3 of treated water (compared to 2.9 to 3.7 kW/m 3 for RO). Scalability – During Phase II, we increased the electrode size from 3.8 cm 2 single-sided electrodes to 180 cm 2 double-sided electrodes. Using larger acid baths and CVD furnace, we increased electrode fabrication capacity increased by 315 times. Scalable electrochemical CDI stack design and balance of plant – During Phase II, we demonstrated at scalable low-pressure drop stack design and balance of plant for the continuous removal of ions. Corrosion Resistance – Based on accelerated corrosion testing data, our high-quality graphitic electrodes have a significantly improved corrosion resistance. This was 20 times better corrosion resistance than our Phase I electrodes and significantly higher than typical CDI system electrodes. Flexibility –By tuning the pore size of the electrode materials, we demonstrated the removal of key target ionic contaminants, such as sodium chloride, nitrate, and phosphate salts. These ionic contaminants are common in agricultural and industrial wastewater runoff and are difficult to remove by conventional methods, which require excessive use of reagents.

Cox, Dr. Philip↗

DOE OSTI2011

THE POTENTIAL OF NANOPARTICLE ENHANCED IONIC LIQUIDS (NEILS) AS ADVANCED HEAT TRANSFER FLUIDS

Interest in capturing the energy of the sun is rising as demands for renewable energy sources increase. One area of developing research is the use of concentrating solar power (CSP), where the solar energy is concentrated by using mirrors to direct the sunlight towards a collector filled with a heat transfer fluid (HTF). The HTF transfers the collected energy into pressurized steam, which is used to generate energy. The greater the energy collected by the HTF, the more efficent the electrical energy production is, thus the overall efficiency is controlled by the thermal fluid. Commercial HTFs such as Therminol{reg_sign} (VP-1), which is a blend of biphenyl and diphenyl oxide, have a significant vapor pressure, especially at elevated temperatures. In order for these volatile compounds to be used in CSP systems, the system either has to be engineered to prevent the phase change (i.e., volatilization and condensation) through pressurization of the system, or operate across the phase change. Over thirty years ago, a class of low-melting organic compounds were developed with negligible vapor pressure. These compounds are referred to as ionic liquids (ILs), which are organic-based compounds with discrete charges that cause a significant decrease in their vapor pressure. As a class, ILs are molten salts with a melting point below 100 C and can have a liquidus range approaching 400 C, and in several cases freezing points being below 0 C. Due to the lack of an appreciable vapor pressure, volatilization of an IL is not possible at atmospheric pressure, which would lead to a simplification of the design if used as a thermal fluid and for energy storage materials. Though the lack of a vapor pressure does not make the use of ILs a better HTF, the lack of a vapor pressure is a compliment to their higher heat capacity, higher volummetric density, and thus higher volumetric heat capacity. These favorable physical properties give ILs a pontential advantage over the current commerically used thermal fluids. Also within the past decade nanofluids have gained attention for thermal conductivity enhancment of fluids, but little analysis has been completed on the heat capacity effects of the nanoparticle addition. The idea of ILs or nanofluids as a HTF is not new, as there are several references that have proposed the idea. However, the use of ionic liquid nanofluids containing nanomaterials other than carbon nanotubes has never before been studied. Here, for the first time, nano-particle enhanced ILs (NEILs) have been shown to increase the heat capacity of the IL with no adverse side effects to the ILs thermal stability and, only at high nanoparticle loading, are the IL physical properties affected. An increase of volumetric heat capacity translates into a better heat transfer fluid as more energy is stored per volumetric unit in the solar concentrating section, thus more efficency in increased steam pressure. Results show that the properties of the NEIL are highly dependant on the suspended nanomaterial and careful materials selection is required to fully optimize the nanofluid properties.

14 SOLAR ENERGY↗

DOE OSTI2012

Foundation Heat Exchanger Final Report: Demonstration, Measured Performance, and Validated Model and Design Tool

Geothermal heat pumps, sometimes called ground-source heat pumps (GSHPs), have been proven capable of significantly reducing energy use and peak demand in buildings. Conventional equipment for controlling the temperature and humidity of a building, or supplying hot water and fresh outdoor air, must exchange energy (or heat) with the building's outdoor environment. Equipment using the ground as a heat source and heat sink consumes less non-renewable energy (electricity and fossil fuels) because the earth is cooler than outdoor air in summer and warmer in winter. The most important barrier to rapid growth of the GSHP industry is high first cost of GSHP systems to consumers. The most common GSHP system utilizes a closed-loop ground heat exchanger. This type of GSHP system can be used almost anywhere. There is reason to believe that reducing the cost of closed-loop systems is the strategy that would achieve the greatest energy savings with GSHP technology. The cost premium of closed-loop GSHP systems over conventional space conditioning and water heating systems is primarily associated with drilling boreholes or excavating trenches, installing vertical or horizontal ground heat exchangers, and backfilling the excavations. This project investigates reducing the cost of horizontal closed-loop ground heat exchangers by installing them in the construction excavations, augmented when necessary with additional trenches. This approach applies only to new construction of residential and light commercial buildings or additions to such buildings. In the business-as-usual scenario, construction excavations are not used for the horizontal ground heat exchanger (HGHX); instead the HGHX is installed entirely in trenches dug specifically for that purpose. The potential cost savings comes from using the construction excavations for the installation of ground heat exchangers, thereby minimizing the need and expense of digging additional trenches. The term foundation heat exchanger (FHX) has been coined to refer exclusively to ground heat exchangers installed in the overcut around the basement walls. The primary technical challenge undertaken by this project was the development and validation of energy performance models and design tools for FHX. In terms of performance modeling and design, ground heat exchangers in other construction excavations (e.g., utility trenches) are no different from conventional HGHX, and models and design tools for HGHX already exist. This project successfully developed and validated energy performance models and design tools so that FHX or hybrid FHX/HGHX systems can be engineered with confidence, enabling this technology to be applied in residential and light commercial buildings. The validated energy performance model also addresses and solves another problem, the longstanding inadequacy in the way ground-building thermal interaction is represented in building energy models, whether or not there is a ground heat exchanger nearby. Two side-by-side, three-level, unoccupied research houses with walkout basements, identical 3,700 ft{sup 2} floor plans, and hybrid FHX/HGHX systems were constructed to provide validation data sets for the energy performance model and design tool. The envelopes of both houses are very energy efficient and airtight, and the HERS ratings of the homes are 44 and 45 respectively. Both houses are mechanically ventilated with energy recovery ventilators, with space conditioning provided by water-to-air heat pumps with 2 ton nominal capacities. Separate water-to-water heat pumps with 1.5 ton nominal capacities were used for water heating. In these unoccupied research houses, human impact on energy use (hot water draw, etc.) is simulated to match the national average. At House 1 the hybrid FHX/HGHX system was installed in 300 linear feet of excavation, and 60% of that was construction excavation (needed to construct the home). At House 2 the hybrid FHX/HGHX system was installed in 360 feet of excavation, 50% of which was construction excavation. There are six pipes in all excavations (three parallel circuits - out and back), and the multiple instances of FHX and/or HGHX are all connected in series. The working fluid is 20% by weight propylene glycol in water. Model and design tool development was undertaken in parallel with constructing the houses, installing instrumentation, and monitoring performance for a year. Several detailed numerical models for FHX were developed as part of the project. Essentially the project team was searching for an energy performance model accurate enough to achieve project objectives while also having sufficient computational efficiency for practical use in EnergyPlus. A 3-dimensional, dual-coordinate-system, finite-volume model satisfied these criteria and was included in the October 2011 EnergyPlus Version 7 public release after being validated against measured data.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2012

Foundation Heat Exchanger Final Report: Demonstration, Measured Performance, and Validated Model and Design Tool

15 GEOTHERMAL ENERGY↗

NASA NTRS2014

Preliminary Sensorimotor and Cardiovascular Results from the Joint Russian and U.S. Pilot Field Test with Planning for the Full Field Test Beginning with the Year Long Intenational Space Station

Ongoing collaborative research efforts between NASA's Neuroscience and Cardiovascular Laboratories, and the Institute of Biomedical Problems' (IBMP) Sensory-Motor and Countermeasures Laboratories have been measuring functional sensorimotor, cardiovascular and strength responses following bed rest, dry immersion, short duration (Space Shuttle) and long duration (Mir and International Space Station) space flights. While the unloading paradigms associated with dry immersion and bed rest does serve as acceptable flight analogs, testing of crew responses following the long duration flights previously has not been possible until a minimum of 24 hours after landing. As a result, it is not possible to estimate the nonlinear trend of the early (<24 hr) recovery process, nor is it possible to accurately assess the full impact of the decrements associated with long duration flight. To overcome these limitations, both the Russian and U.S. sides have implemented testing at landing site. By joint agreement, this research effort has been identified as the functional Field Test (FT). For practical reasons the FT has been divided into two phases: the full FT and a preliminary pilot version (PFT) of the FT that is reduced in both length and scope. The primary goal of this research is to determine functional abilities in long duration space flight crews beginning as soon after landing as possible (< 2 hr) with one to three immediate follow-up measurements on the day of landing. This goal has both sensorimotor and cardiovascular elements, including evaluations of NASA's new anti-orthostatic compression garment and the Russian Kentavr garment. Functional sensorimotor measurements will include, but are not limited to, assessment of hand/eye coordination, ability to egress from a seated position, walk normally without falling, measurement of dynamic visual acuity, ability to discriminate different forces generated with both the hands and legs, recovery from a fall, a coordinated walk involving tandem heel-to-toe placement, and determination of postural ataxia while standing. The cardiovascular portion of the investigation includes blood pressure and heart rate measurements during a timed stand test in conjunction with postural ataxia testing (quiet stance sway) as well as cardiovascular responses during other functional tasks. In addition to the immediate post-landing collection of data for the full FT, postflight data will be acquired at a minimum of one to three more other times within the 24 hr following landing and continue until functional sensorimotor and cardiovascular responses have returned to preflight normative values. The PFT represents a single trial run comprised of jointly agreed upon subset of tests from the full FT and relies heavily on IBMP's Sensory-Motor and Countermeasures Laboratories for content and implementation. The PFT was first conducted following the September 2013 landing of the Soyuz spacecraft (34S) and again following the landing of Soyuz 35S in November. Testing included: (1) a sit-tostand test, (2) recovery from a fall where the crewmember began in the prone position on the ground and then stood for 3 min while cardiovascular stability was determined and postural ataxia data were acquired, and (3) a tandem heel-to-toe walk test to determine changes in the central locomotor program. Video, cardiovascular parameters (heart rate and blood pressure), data from body-worn inertial sensors and severity of postflight motion sickness were collected for analysis. In summary, the level of functional deficit is expected to be most profound during the acquisition of gravity loads immediately after landing when the demands for crew intervention in response to emergency operations will be greatest. Clearly measureable performance parameters such as ability to perform a seat egress, recover from a fall or the ability to see clearly when walking, and related physiological data (orthostatic responses) are required to provide an evidence base for characterizing programmatic risks and the degree of variability among crewmembers for exploration missions where the crew will be unassisted after landing. Overall, these early functional and related physiological measurements will allow estimation of nonlinear sensorimotor and cardiovascular recovery trends to an accuracy that has not been previously captured in over 50 years of space flight.

Reschke, M. F.↗