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Final Report for Project DE-FG02-05ER15718 Fluoropolymers, Electrolytes, Composites and Electrodes

This report is for a project that was initiated under the title “New Proton-Conducting Fluoropolymer Electrolytes for PEM Fuel Cells”, as part of the DOE program titled “Basic Research for the Hydrogen Fuel Cell Initiative”, Program Notice DE-FG01-04ER04-20. The project received 750,000 dollars in initial funding for a three-year term with a start date of August 15, 2005. Creager was PI and co-PIs were DesMarteau and Smith, all from Clemson. The project was renewed for a second three-year term with a start date of June 15 2008, again for 750,000 dollars, with the new title, “Fluoropolymers, Electrolytes, Composites and Electrodes”. Shortly after the renewal was put in place, co-PI Smith left Clemson to accept a position at the University of Texas at Dallas. After a period of no-cost extension the project was renewed on January 1 2013 for another three-year term, this time for a smaller amount ($525,000) and with Thrasher, a new senior hire at Clemson, as co-PI in place of Smith. DesMarteau had retired from Clemson by this time but was retained as a project advisor. After a final one-year no-cost extension for calendar year 2016, the project ended on December 31, 2016, giving it an active period of eleven and one-half years, from August 15 2005 to December 31 2016. The overall objective of this research project has been to create and understand the behavior of new fluoropolymer-based electrolytes and electrodes suitable for use in electrochemical energy storage and conversion devices. The objective was pursued via research on new fluorinated monomers, new polymers and polyelectrolytes (also known as ionomers), and new electrocatalyst supports that in some cases include chemically grafted electrolytes to promote rapid ion transport to electrocatalytically active sites (usually platinum nanoparticles) on the support. The research involved synthesis and characterization of new materials, and creation and use of new measurement techniques that address key properties of the materials, e.g. mixed electronic / ionic conduction in the absence of liquid electrolyte, that are relevant to their use in energy conversion and storage.

30 DIRECT ENERGY CONVERSION↗

A New Remote Communications Link to Reduce Residential PV Solar Costs

Monitoring of PV/DER site production is expensive to install and unreliable. Among third party systems providers, lost communications links are a growing concern. Nearly 20% of links are failing, provisioning is complex, recovery is expensive, production data is lost, and access is fragmented. FleetLink is a new concept in DER system communications, purpose built for lowering the cost of maintaining active contact with residential end user sites and ensuring that production data is reliably available to third party systems providers. Systems providers require accurate, secure system monitoring and reporting of production data and system faults while driving down overall costs to compete effectively. This plug and play, independently operating communications solution lowers the cost of fleet contact from typically .08 dollars-$.12/W down to .02 dollars -.03/W including installation and maintenance expenses. FleetLink establishes a breakthrough in simplicity that facilitates rapid expansion of residential solar by reducing initial capital outlay and lowering installation labor time and skill levels. The solution also facilitates higher DER installation growth rates by driving down maintenance costs and eliminating communications trouble calls. This is accomplished by the FleetLink’s unique network technology that enables dynamic network configuration for fast changes, and active, self-healing DER site contact for uptime assurance. Using an open source network framework with proprietary, application specific enhancements, FleetLink independently manages connectivity, security, recovery, grid control communications, and fleet expansion while presenting a compliant SunSpec interface to the third party operations centers. The net system cost savings of at least .05 dollars/W supports the SunShot cost goals and the flexibility and scalability of the solution accelerates the velocity and ubiquitous adoption of solar.

14 SOLAR ENERGY↗

Coeur d’Alene Tribe Benewah Market Energy Efficiency Project Final Technical Report

The Coeur d’Alene Reservation has been the home of the Coeur d’Alene Tribe since time immemorial and it is fitting that the Tribe’s name in the Coeur d’Alene language is schitsu’umsh, “the ones who were found here.” The Reservation is located in northern Idaho, is approximately 345,000 acres and is comprised of forest land, agricultural land, several streams, Coeur d’Alene Lake and the St. Joe River and a small amount of developed land. The project area was conducted within the boundaries of the Coeur d’Alene Reservation. The population of the Reservation is 6,760 (2010 Census). Currently, there are approximately 2,463 enrolled Coeur d’Alene Tribal members (Coeur d’Alene Tribe Enrollment 2016). The Benewah Market is a Tribally-owned and operated facility located at 1111 B St. Plummer, ID 83851. The Benewah Market is an approximately 23,500 square foot single-story structure. The majority of the building is occupied by a grocery store with a full meat department, deli, and bakery. Approximately 20% of the floor area at the northeast corner is occupied by an Ace Hardware retailer. The largest part of the building is approximately 17,000 square feet, is separately metered and houses the grocery store which was constructed in 1984. The market is the largest full service market serving the Coeur d’Alene Reservation and is the only full service market in a 35-mile radius. The Tribe has benefited greatly from the Benewah Market Energy Efficiency Project and will continue to do so for many years: The health and safety of the food has been improved greatly now that the refrigeration and freezer cases are at a constant and safe temperature on a monitoring and alarm system. There is no longer a thaw and freeze cycle that allows fluctuations in temperature. If the power goes out, there is an immediate alarm and contact so that time may be tracked and food kept safe during an outage. The overall annual energy use in the Benewah Market has dropped by 22.9% -Energy costs for the Market decreased by an estimated 11,620 dollars in one year due to this project. The Tribe has seen an increase in the cost of energy from Plummer Power and this was offset by the reduction in energy consumed. This estimate assumes that the Tribe would have consumed the same amount of energy as the prior year. -Maintenance costs are estimated to have decreased by $10,000 in just the one year since installation in contract repair and maintenance. The Tribe estimates that it has saved 24,000 dollars over a one-year time period in labor costs to maintain the older system. Due to having a more efficient store, with safer, more attractive display of food and lower energy and maintenance costs, the store is able to be more viable economically. The store has increased its sales and has been able to pass along operations and maintenance savings to its customers and employees. The Tribe hosted a ribbon-cutting ceremony on February 28, 2017 at the Benewah Market with Chris Deschene, then Office of Indian Energy Director, as well as representatives from the Coeur d’Alene Tribe and Bonneville Power Administration. While the ribbon-cutting ceremony was going on, the Tribe’s media outlets covered the ceremony and placed information about the project on the Tribe’s Facebook page on two separate occasions. The Coeur d’Alene Tribe’s Natural Resources Department and the Tribe’s Development Corporation are thankful for the opportunity that the Benewah Market Energy Efficiency Project has afforded the Coeur d’Alene Tribal community. Without the U.S. Department of Energy’s Indian Energy Program funding and its dedicated staff, this project would not have been completed. This has been a lot of work for all parties involved but has provided benefits to thousands of people for many years to come.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Innovative Patient Room Lighting System with Integrated Spectrally Adaptive Control

In December of 2013, the U.S. Department of Energy’s SSL R&D Program released a Funding Opportunity Announcement (FOA), that for the first time, contained opportunities for comprehensive application-specific system development. The FOA included opportunities for two applications, one of which was a Patient Room. Philips Lighting Research North America, submitted a proposal for the Patient Room application, and was selected for the complete project award. The award amount was for $497,127, with a Philips Research co-funding commitment 165,709 dollars. The total project value was 662,836 dollars. This project sought to redefine lighting for the patient room application. The goal was to deliver an innovative LED patient suite (patient room and bathroom) lighting system solution that was 40% more energy-efficient than traditional fluorescent incumbent technologies, and would meet all the visual and non-visual needs of patients, caregivers and visitors, and improve the patient experience. State-of-the-art multichannel LED platforms and control technologies that would provide spectral tuning and become part of an intelligent, connected lighting system drove the solution. The project was scoped into four main task areas that included a) System Concept Creation, b) Identification of the Luminaire Portfolio, c) Development of the Connected Lighting Infrastructure, and d) System Performance Validation. Each of the four main tasks were completed and validated extensively over the course the 2 ½ year project. The system concept was created by first developing a lighting design that demonstrated best practices for patient room lighting – illuminance and uniformity for task performance, reduced glare, and convenient controls, in addition to giving patients control over the lighting in their environment. A framework was defined to deliver circadian support via software behaviors. Through that process luminaires were identified from the Philips portfolio that were adaptable – by their form, dimensions, and optical materials – to mix multicolor LED platforms uniformly and deliver target design lumen levels. The Blue Sky luminaire was selected for the patient bed area to give the illusion of skylight while providing white light on the patient bed. Luminaires used existing 2-channel tunable white LED boards, and newly developed 4-channel LED boards. Red-Orange, Blue, Green, and Blue-shifted Yellow LED chips were selected based on spectral characteristics and their ability to produce high quality white light. 4-channel Power over Ethernet (PoE) drivers were developed and firmware written so they would communicate with both 2- and 4-channel boards. These components formed the backbone of the connected lighting infrastructure. Software, flexible and nuanced in its complexity, was written to set behaviors for myriad lighting scenes in the room throughout the 24 hour day – and all could be overridden by manual controls. This included a dynamic tunable white program, three color changing automatic programs that simulated degrees of sunrise to sunset palettes, and an amber night lighting system that offered visual cues for postural stability to minimize the risk of falls. All programs were carefully designed to provide visual comfort for all occupants, support critical task performance for staff, and to support the patient’s 24hr rhythms. A full scale mockup room was constructed in the Philips Cambridge Lab. The lighting system was installed, tested and functionality demonstrated to ensure smooth operation of system components – luminaires, drivers, PoE switches, wall controls, patient remote, and daylight and occupancy sensors. How did the system perform? It met visual criteria, confirmed by calculations, simulations and measurements in the field. It met non-visual criteria, confirmed by setting circadian stimulus (CS) targets and performing calculations using the calculator developed by the Lighting Research Center. Finally, human factors validation studies were conducted to gain insight from real end users in the healthcare profession; surveys were administered, data analyzed, and audio comments captured. The general consensus was positive, with requests to pilot the system in their hospitals. The importance of the research completed under this grant is that it allowed the exploration and development of a unique lighting system, one that would deliver a blend of visual and non-visual criteria in patient room design for today’s healthcare environment. The research investigated the area of multichannel LED technology, multichannel Power over Ethernet (PoE) drivers and their integration with automatic and manual controls as a system – uncovering and meeting challenges along the way. It married visual needs of patients and staff with support for 24 hour rhythms, placing value on the wellbeing of the patient – while successfully saving energy over incumbent technologies. Indications are that the market is ready and willing to invest – multiple healthcare facilities are in line to pilot this system, recognizing its value beyond energy to patient and staff well-being. Its value to the public can best be expressed by a patient support coordinator who, after spending several hours in the room being immersed in the lighting, analyzing all its features, commented: “This re-writes lighting for healthcare”.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

An Integrated Supercritical System for Efficient Produced Water Treatment and Power Generation

The main goal of this project was to evaluate the feasibility of an integrated supercritical (SC) water desalination and power generation system for treatment of produced waters from CO 2 sequestration, oil production, and coal-bed methane recovery. This system may offer a transformative approach to generating power from coal or natural gas (NG) and purifying saline water or produced water with high total dissolved solids (TDS) in a zero-liquid discharge plant. The closed-loop steam cycle of conventional power plants was replaced with an open-loop steam cycle that heated the pretreated produced water above the SC point of water (374 °C and 221 bar) to precipitate and separate the salts dissolved in the water. After separation of the precipitated salt, the SC steam required further treatment to reduce the salt content from ~100 mg/L (ppm) to <1 ppm to make it suitable for use in turbines for power generation. A SC membrane distillation unit was used to polish the SC steam, which could be sent through a series of turbines for power generation, and the steam exiting the low-pressure turbine could be condensed by cooling water to produce pure water. Project tasks included a process simulation and a techno-economic evaluation of the integrated system; design and assembly of SC salt precipitation and membrane distillation systems; development and characterization of advanced carbon membranes for SC membrane distillation; and pretreatment, desalination, and purification of different produced water samples with salt concentrations of 30,000–200,000 ppm to a high-purity (<1 ppm) level. Process simulations were performed for 550 MW SC coal-fired or NG baseline cases and various scenarios for the proposed integrated SC system using produced water as the water source and coal or NG as the fuel source. Simulation results indicated that the net plant efficiency loss of the proposed SC cogeneration process would be in the range of <1% to ~4%, in which NG and lower TDS produced water cases would have higher efficiencies. The proposed process for coal-fired cases could provide all water needs for the power generation process and generate additional pure water for beneficial use. A techno-economic analysis was performed to estimate the cost of produced water treatment (dollars /kgal of treated water) by conventional treatment processes compared with the proposed cogeneration process. The cost estimation for the proposed cogeneration system included the cost of pretreatment, the cost of power loss to integrate the water desalination process into the power generation system, and the cost of plant modification or retrofitting. The cost of produced water treatment was calculated by assuming three different scenarios in which converting a baseline power plant to the proposed cogeneration plant would increase the cost of the boiler and feed water system by 10%, 50%, and 100%. Results indicated that the cost of produced water treatment, even with a 100% cost increase, was in the range of $8.6–11.6 dollars per kgal, which is about half of the treatment cost by conventional methods. The cost of produced water treatment by the proposed cogeneration system could be further reduced or a considerable income could be generated if the values of saltwater and freshwater products are considered. Overall, the techno-economic analysis results indicated that the proposed integrated SC system could potentially treat produced water at a cost significantly lower than the cost of produced water treatment by conventional technologies. To evaluate the feasibility of the proposed treatment system at a laboratory scale, a SC salt precipitation and membrane distillation system was designed and fabricated to treat a simulated brine or pretreated produced water by precipitating salts and further polishing the SC steam containing ~100 ppm salts to a high-purity steam. Through baseline tests with NaCl solutions, with concentrations ranging from 30,000 to 200,000 ppm, it was demonstrated that concentrated feed solutions could be treated by precipitating salt at SC conditions to a TDS level of 130 ppm. Produced water samples were collected from a potential CO 2 sequestration site, a coal-bed methane site, and an oilfield in Illinois. Representative samples were characterized for various water quality parameters, including pH; turbidity; conductivity; and concentrations of selected anions, cations, alkalinity, dissolved organic carbon, total suspended solids, TDS, and total petroleum hydrocarbons. The produced water samples were first treated by conventional pretreatment methods to remove residual oil, dissolved organic matter, and scale-forming species. Pretreatment methods included coagulation, sedimentation, filtration, activated carbon adsorption, and ion-exchange adsorption. Pretreated produced waters were treated at SC conditions in which salts were precipitated. Analysis of treated samples revealed that the concentration of Na (the main cation) in produced waters was reduced dramatically from 14,000–47,400 ppm in the feed to 21–80 ppm in treated waters. Concentrations of other main cations (Ca, Mg, Sr, K) also decreased significantly from initial values of ~1,000–22,000 ppm to ~1 ppm or less. However, a significant increase in the concentrations of Fe, Ni, Cu, and Co was observed, mainly caused by leaching of these elements from the system (vessels, filters, tubing), which is manufactured from alloys containing Fe, Ni, Cu, and Co. To polish the SC steam containing a salt content of ~100 ppm to a high-purity level of <1 ppm, a SC membrane distillation treatment using carbon membranes was employed. Different types of self-standing or supported carbon membranes were developed from graphite, graphene, carbon nanotubes, carbon nanofibers, and pyrolytic carbon. Screening tests revealed that only a limited number of developed carbon membranes were suitable for the purification of steam at SC conditions. Membranes that were either fragile and lacked mechanical strength or had large pores and showed limited salt rejection (<20%) were found to be unsuitable for the purification of SC steam. Promising carbon membranes that were successfully tested for purifying SC steam included two graphite membranes (i.e., AF-5, a porous graphite material, and FGS, a flexible graphite sheet) and a carbon nanotube membrane grown on a Hastelloy substrate and then further modified using a proprietary method (i.e., membrane C). The AF-5 membrane exhibited a stable water flux of ~50 kg/m 2 ∙h and ~40% salt rejection. The FGS membrane had a high salt rejection of 95%–98% but a lower water flux of ~15 kg/m 2 ∙h. Membrane C showed an extremely high flux of 200-800 kg/m 2 ∙h, which is one order of magnitude higher than the water flux of conventional membranes. Membrane C also exhibited 87%–93% salt rejection. Overall, a two-stage or multistage polishing treatment by these membranes could lower the salt content of the SC steam from initial values of ~100–200 ppm to the steam quality of <1 ppm or to parts per billion levels required for the power cycle.

20 FOSSIL-FUELED POWER PLANTS↗

A Modular and Flexible High-Frequency-Link Transformer with a Reduced Device Count and Zero High-Side Devices

In general, large power transformers (LPTs) are not interchangeable with each other and their high costs prohibit extensive spare inventories more so considering that on an average only 1.3 LPTs are manufactured for individual design. The latter pose a further challenge since given that the several existing LPTs are reaching their end of service lives, loss of plurality of such LPTs, that form the backbone of U.S. power grid, will clearly run into the problem of energy security related to the non-availability of sufficient spares (and extended lead time) exacerbated further by the fact that these spares are not interchangeable for installations at different locations. Conventional LPT cost millions of dollars and weighs significantly between approximately 100 and 400 tons. Two raw materials—copper and electrical steel—account for over 50 percent of the total cost of an LPT. In recent years, the price volatility of these two commodities in the global market has affected the manufacturing conditions and procurement strategy for LPTs. Transportation is also an important element of the total LPT cost, because an LPT can weigh significantly and often requires long-distance transport. Transporting an LPT is challenging—its large dimensions and heavy weight pose unique requirements to ensure safe and efficient transportation. Current road, rail, and port conditions are such that transportation is taking more time and becoming more expensive. Conventional low-frequency LPTs typically follow a monolithic approach to design due to historical reasons that need to transition to more modular and flexible (e.g., in voltage, impedance, and power flow) designs with ability to seamlessly/near-seamlessly scale. They should also have the ability to incorporate new technologies without in all cases redoing a LPT design from scratch. Given that the cost of raw materials has continued to increase, next-generation LPTs need to pursue avenues for reducing these costs. An added necessity is to reduce the transportability cost, which is significant in conventional LPTs. Further, given that LPTs are for the long term, they need to be durable, efficient, and fault tolerant with overloading capability. Given this backdrop, the objective and accomplishment of this one-year DOE (SPONSOR) R&D project, led by small business NextWatt LLC (PRIME, Lead PI: Dr. Sudip K. Mazumder) and University of Arkansas at Fayetteville (SUBAWARDEE, PI: Dr. Juan Balda) were to explore the design of a (8 – 20 kHz) high-frequency-link (HFL) based 100-MVA LPT with nominal voltage of 115/69 kV, with $15 - $22 dollars US per kVA when manufactured in “moderate” volume, with 99% energy-conversion efficiency, with 300% reduction in both volume and weight compared to a conventional LPT with the same electrical ratings, with impedance variation greater than 5%, with direct AC/AC power conversion capability, with very-high energy-conversion efficiency (using wide-bandgap SiC based field effect MOSFET devices) over a wide operating temperature, with reduction in both volume and weight with regard to conventional low frequency LPT, and with significant reduction in number of devices compared to state of the art solid state transformer topology.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Cost and Performance Baseline for Fossil Energy Plants Supplement: Sensitivity to CO 2 Capture Rate in Coal-Fired Power Plants

The cost and performance of various plants designed to meet a range of carbon dioxide (CO 2 ) emissions are evaluated in this report by varying the CO 2 capture rate. The base cases for these designs are the supercritical (SC) pulverized coal (PC) plant from the National Energy Technology Laboratory’s (NETL) report “Cost and Performance Baseline for Fossil Energy Plants, Volume 1a: Bituminous Coal (PC) and Natural Gas to Electricity, Revision 3” and the General Electric Energy (GEE) integrated gasification combined cycle (IGCC) plant in NETL’s report, “Cost and Performance Baseline for Fossil Energy Plants, Volume 1b: Bituminous Coal (IGCC) to Electricity, Revision 2 – Year Dollar Update.” The chosen SC PC plants were based on the Case B12B, differing only in the addition of a bypass flow path that allows for an appropriate portion of the flue gas stream exiting the desulfurization step to be directed towards the stack, which reduces the amount CO 2 captured in the Cansolv process. The chosen IGCC plants were based on the Case B5B, differing by bypassing (either partially or entirely) the water gas shift reactors and thereby reducing the amount of CO 2 captured in the Selexol process. The major components of the underlying CO 2 capture technology in the plants were preserved with minimal modifications to the overall processes. The SC PC cases include up-to-date cost and performance information from recent vendor quotes whereas the IGCC performance and cost are based upon the older quotes used for the Revision 2 report, with standard adjustments made to update the costs to 2011 dollars.

01 COAL, LIGNITE, AND PEAT↗

Demonstration of High-Temperature Calcium-Based Thermochemical Energy Storage System for use with Concentrating Solar Power Facilities

Thermochemical energy storage (TCES) systems offer several advantages over sensible heat storage via molten salts for concentrating solar power (CSP) including: energy density, cost, indefinite storage time, and no risk of freezing. SR’s TCES system utilizes a CaO-based carbonation reaction at high temperature in a fixed bed heat exchanger reactor. The SunShot APOLLO project focuses on the validation of the calcium oxide sorbent for capacity, durability, system economics, and demonstration of the system at a small pilot scale, including system control and operation in simulated on-sun conditions, discharging at 720°C. Under phase I SR completed evaluation of the sorbent loaded in a single-channel heat exchanger reactor. The major accomplishments of phase II are: Design, fabrication and commissioning of a 4 kWhth pilot plant (50x capacity increase from previous bench scale) with a closed-loop CO 2 system, and a commercially relevant heat exchange reactor. The heat exchange reactor has been designed with state-of-the-art modeling tools to ensure 1) sufficient lifetime of the Incoloy body and 2) performance of the packed bed reactor will be adequate to meet the milestones. The rest of the pilot system has been designed with off-the shelf components to maximize reliability and cost effectiveness. The system is highly instrumented and capable of time resolved, independent measurements of the heat and mass balances respectively. Major developments in the technoeconomic analysis (TEA) include 1) reduction of the cost of membrane gas storage for the near-term and future systems and 2) integration with liquid metal receivers and particle receivers for higher decarbonation temperatures and pressures which reduced the cost of gas compression and increased system efficiency. The result are three scenarios with costs bases of 21.9 dollars, 14.3 dollars, and 10.9 dollars/kWh th corresponding to a real LCOE of 59, 57, 56 dollars/MW he , respectively. The basic operations of the energy storage system were demonstrated for carbonation (discharging) and decarbonation (charging) over short time periods. Excellent control of the CO 2 mass balance across the reactor was achieved with mass flow controllers and the basic operation of the level control of the CO 2 gas bladder was achieved. The system was apparently free from leaks and operated continuously for 18 days with no mechanical failures, thus meeting milestone 2.5.5. The major shortcomings of the system had to do with the controls which prevented us from deep cycling and or reaching high cycles. We were unable to decarbonate (charge) the system for more than a few minutes at a time, which was much shorter than the design target of 10 hrs. This issue could not be resolved due to facility availability and contract closure. One major finding is that CaO-based TCES is most cost efficient when charged with HTF (heat transfer fluid) temperatures >850°C to reach the round-trip exergy efficiency and system cost targets which are higher temperatures than those considered for Gen 3 CSP. Many of the balance of plant components do not exist today, however we are encouraged by our findings that in general with more work we are able to reduce the capital cost, for example with the membrane gas storage, which is an innovative component in itself. The CaO-based TCES system has potential to meet the latest SunShot 2030 goals of LCOE at 50 $/MW he with capital costs of <11/kWh th .

14 SOLAR ENERGY↗

Chippewa Cree Residential Solar Deployment Project

The overall project goal was to install clean energy systems in order to achieve the Chippewa Cree Tribe’s long-term goal of energy self-sufficiency, environmental protection, and better lives for our tribal members and community. This would be the first solar deployment project on the Rocky Boy’s Reservation. With 50% of the funding provided by the Office of Indian Energy, the Chippewa Cree Tribe teamed up with GRID Alternatives to install six grid-tied, solar electric systems for low-income single-family homes. The systems installed were estimated to provide 4,400 kWh annually with an estimated $451 dollar savings per household. After monitoring the systems for a year, we were almost able to obtain our goal with an average of 3,971 kWh and a $419 dollar average savings per household. We would have exceeded our goal but one of the units was without power for the majority of the year bringing down the average significantly. Another major component to the grant was workforce development. GRID Alternatives supplied training for students from Stone Child College on the installation process. With the collaboration and planning efforts from all of the departments, the installations were completed in October of 2016. Throughout the report you will see the six installations are diverse, and each needs to be considered in the context of the individual family structure, size, and energy consumption habits.

14 SOLAR ENERGY↗

Demonstration of High-Temperature Calcium-Based Thermochemical Energy Storage System for use with Concentrating Solar Power Facilities

Thermochemical energy storage (TCES) systems offer several advantages over sensible heat storage via molten salts for concentrating solar power (CSP) including: energy density, cost, indefinite storage time, and no risk of freezing. SR’s TCES system utilizes a CaO-based carbonation reaction at high temperature in a fixed bed heat exchanger reactor. The SunShot APOLLO project focuses on the validation of the calcium oxide sorbent for capacity, durability, system economics, and demonstration of the system at a small pilot scale, including system control and operation in simulated on-sun conditions, discharging at 720°C. Under phase I SR completed evaluation of the sorbent loaded in a single-channel heat exchanger reactor. The major accomplishments of phase II are: Design, fabrication and commissioning of a 4 kWhth pilot plant (50x capacity increase from previous bench scale) with a closed-loop CO 2 system, and a commercially relevant heat exchange reactor. The heat exchange reactor has been designed with state-of-the-art modeling tools to ensure 1) sufficient lifetime of the Incoloy body and 2) performance of the packed bed reactor will be adequate to meet the milestones. The rest of the pilot system has been designed with off-the shelf components to maximize reliability and cost effectiveness. The system is highly instrumented and capable of time resolved, independent measurements of the heat and mass balances respectively. Major developments in the technoeconomic analysis (TEA) include 1) reduction of the cost of membrane gas storage for the near-term and future systems and 2) integration with liquid metal receivers and particle receivers for higher decarbonation temperatures and pressures which reduced the cost of gas compression and increased system efficiency. The result are three scenarios with costs bases of 21.9 dollars, 14.3 dollars, and 10.9 dollars/kWhth corresponding to a real LCOE of 59, 57, 56 dollars/MWhe, respectively. The basic operations of the energy storage system were demonstrated for carbonation (discharging) and decarbonation (charging) over short time periods. Excellent control of the CO 2 mass balance across the reactor was achieved with mass flow controllers and the basic operation of the level control of the CO 2 gas bladder was achieved. The system was apparently free from leaks and operated continuously for 18 days with no mechanical failures, thus meeting milestone 2.5.5. The major shortcomings of the system had to do with the controls which prevented us from deep cycling and or reaching high cycles. We were unable to decarbonate (charge) the system for more than a few minutes at a time, which was much shorter than the design target of 10 hrs. This issue could not be resolved due to facility availability and contract closure. One major finding is that CaO-based TCES is most cost efficient when charged with HTF (heat transfer fluid) temperatures >850°C to reach the round-trip exergy efficiency and system cost targets which are higher temperatures than those considered for Gen 3 CSP. Many of the balance of plant components do not exist today, however we are encouraged by our findings that in general with more work we are able to reduce the capital cost, for example with the membrane gas storage, which is an innovative component in itself. The CaO-based TCES system has potential to meet the latest SunShot 2030 goals of LCOE at 50 dollars/MWhe with capital costs of <11/kWhth.

14 SOLAR ENERGY↗

The Quantum Nature and Mass of the Neutrino. FY20 Annual Laboratory Continuation Progress Report

Over the last 100 years we have learned a much about the neutrino, but there remain interesting questions about this weakly interacting particle. In particular, at LLNL we are developing experiments to measure the mass and the quantum nature of the neutrino. The 2015 long range plan recommended tonne-scale neutrinoless double beta decay experiments as the top new project priority and this experiment will target the quantum nature of the neutrino. The LLNL team is motivated and focused on developing the best technology for this experiment which is a liquid xenon time project chamber called nEXO. On a longer time scale, LLNL is also developing technology to measure the neutrino mass with tritium decay experiments. Work on nEXO at LLNL started in 2015 with an LDRD and program development funds to develop the nEXO concept, publish sensitivity predictions, explore alternatives and risks, and to build a credible project team and this effort is on going. In addition, we received research funding from DOE-SC NP and LLNL manages pre-conceptual R&D for the nEXO collaboration a portion of which is executed at LLNL. The Project 8 effort is solely funded by LLNL LDRD, and ends this year. A second LDRD effort is focused on repurposing cyclotron radiation emission spectroscopy for eV-scale X-ray detection. This second effort, while separated from Project 8, still has scientific and technical commonalities with Project 8. The funding for this X-ray detection effort will continue for one more year. LLNL has a long history of building large projects, science projects and time projection chambers, but nEXO is in fact the first project of this scale that LLNL is prepared to lead for DOE-SC NP.We have the tools, skills, people and motivation to make nEXO a reality. The current program development dollars are used to prepare the nEXO concept for down select and CD1. These internal LLNL dollars pay for a number of things including project staff to organize the nEXO collaboration for the various reviews that lie ahead, to develop the draft plans and structure to manage the project as well as setting up an external advisory committee. The current LDRD is exploring alternatives that effect the risk profile as well as possible performance improvements. The DOE-SC NP base funding is targeted at simulation and analysis of the nEXO concept in preparation for the down select and refinement of the understanding of the detector as well as scientific effort on the large xenon test stand (LXTS) that will burn down one of the largest risks to the nEXO project. Lastly, LLNL is leading the pre-conceptual R&D effort and managing the funds for the nEXO collaboration. The results of this effort are reported elsewhere, but the scope of this executed at LLNL will be reported here and is primarily the engineering and construction of the LXTS experiment. The primary technical contribution of LLNL to the Project 8 concept is the formation and study of atomic tritium. Atomic tritium is necessary for Project 8 to reach the ultimate sensitivity. LLNL has considerable experience with tritium and is well suited for this crucial work. Although the focus of this work is strictly fundamental science, there has already been one significant spinoff to develop a new means to measure radio xenon in the air

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The Quantum Nature of the Neutrino

Over the last 100 years we have learned much about the neutrino, but there remain interesting questions about this weakly interacting particle. In particular, at LLNL we are developing an experiment to measure the quantum nature of the neutrino. The 2015 long range plan recom mended tonne-scale neutrinoless double beta decay experiments as the top new project priority and this experiment will target the quantum nature of the neutrino. The LLNL team is motivated and focused on developing the best technology for this experiment which is a liquid xenon time projection chamber called nEXO. Work on nEXO at LLNL started in 2015 with an LDRD and program development funds to de velop the nEXO concept, publish sensitivity predictions, explore alternatives and risks, and to build a credible project team and this effort is on going. In addition, we received research funding from DOE-SC NP and LLNL manages pre-conceptual R&D for the nEXO collaboration a portion of which is executed at LLNL. LLNL has a long history of building large projects, science projects and time projection chambers, but nEXO is in fact the first project of this scale that LLNL is prepared to lead for DOE-SC NP. We have the tools, skills, people and motivation to make nEXO a reality. The current program devel opment dollars are used to prepare the nEXO concept for down select and CD1. These internal LLNL dollars pay for a number of things including project staff to organize the nEXO collaboration for the various reviews, to develop the draft plans and structure to manage the project as well as setting up external advisory committees. The DOE-SC NP base funding is targeted at simulation and analysis of the nEXO concept in preparation for the down select and refinement of the under standing of the detector as well as scientific effort on the large xenon test stand (LXTS) that will burn down one of the largest risks to the nEXO project. Lastly, LLNL is leading the pre-conceptual R&D effort and managing the funds for the nEXO collaboration. LLNL continues to build the best scientific team for nEXO and this year that includes adding Ethan Bernard to lead the efforts on the LXTS. We will also soon add a new postoc, Samuel Hedges, in the fall to the LLNL nEXO team. The effort this year was influenced by the portfolio review, and there were a number of scientific activities led by LLNL to prepare for this review. In addition, we again took a lead role on the new sensitivity paper as well as publishing a paper based analyzing the effects of skin xenon in nEXO. LLNL leads the software and analysis for the project and we continued work in this area as well. High voltage remains a significant risk for the project and we continue to make progress on the LXTS that will mitigate this risk. Lastly we remain active in looking at how to scale the technology to larger scales, and expect to produce a paper on this topic in the near future.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Basic Research Needs for Communicating Basic Science

Basic science—also known as discovery or foundational research—is the fuel that powers our innovation ecosystem and the global economy. Despite this critical role, public awareness for how and where basic research is done, how it is funded, and its need for sustainable support over the long term is negligible. The ability to engage broader publics in awareness and understanding of basic science is paramount if we are to maintain the research enterprise that has transformed the modern world. Communicating how the federal government stewards taxpayer dollars for basic science is also incumbent on the agencies and scientists who use public dollars for their research. However, science communication is a complex activity that requires advanced planning, resources, and skill. Therefore, it is important to understand what we know about communicating basic science to the broader publics, as well as what we do not know, to be strategic and better equipped for effective, meaningful engagement. To identify and explore knowledge gaps in our understanding of basic science communication, the Science Public Engagement Partnership (SciPEP), a public-private partnership of the U.S. Department of Energy (DOE) Office of Science and The Kavli Foundation, carried out a two-part landscape analysis: literature surveys of social science scholarship and a basic research needs conference.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

Material Characterization for Large Scale Additive Manufacturing (AM)

The objective of this project was to enable prediction of residual stresses and warpage for extrusion deposition additive manufacturing (EDAM) fabricated carbon fiber thermoplastic matrix parts with three different materials systems produced by Techmer. The materials selected include Polyphenylene sulfide reinforced with 50% by weight of carbon fiber (CF-PPS), Polyethersulfone reinforced with 25% by weight of carbon fiber (CF-PESU), Polysulfone reinforced with 25% by weight of carbon fiber (CF-PSU). ADDITIVE3D © , a physics-based simulation workflow for EDAM, provided the simulation capabilities required for this project. Simulation predictions were validated against measurements carried out during and after the printing process carried out in the CAMRI and LSAM systems . Predictions for temperature, degree of crystallinity and deformation were carried out for the three material systems and two different geometries. Predictions for temperature were correlated very well with the experimental measurements for the two geometries printed using the three-material systems. The crystallinity level was verified for CF-PPS. The predictions for part deformation were in good agreement with the experimental measurements. In the best-case, predictions were within 8% of the maximum displacement observed in the 3-direction whereas predictions were within 14% for the worst-case. The adoption of this technology in commercial large-scale EDAM production processes would dramatically reduce the costs associated with producing articles by that process. Many thousands of dollars in materials, energy, and machine time could be saved by utilizing this simulation technology to develop articles rather than iterative printings to arrive at the optimal or correct design. The avoidance of a single failed print has the possibility of saving tens of thousands of dollars involved in the cost of material, machine and operators’ time.

36 MATERIALS SCIENCE↗

A Novel Process for Carbon Dioxide Conversion to Fuel

In this project, TDA developed a new mixed metal oxide-based sorbent that converts CO2 (captured from coal fired power plants) to CO, which can then be combined with renewable H2 generated by water electrolysis or H2 from steam methane reforming to produce different liquid fuels. TDA’s absorbent-based CO2 conversion process uses a redox process, which splits the catalytic reforming of methane with CO2 reaction into two stages: CO2 reduction to CO and CH4 reforming into H2 and CO which eliminates the equilibrium limitations. The CO produced in the two-stage reactor system can then be further reacted with renewable H2 to produce methanol, naphtha, diesel, or gasoline. We worked with the Advanced Power & Energy Program (APEP) of University of California, Irvine (UCI) to design and develop the liquid fuel synthesis process that is built around this new material. We demonstrated the techno-economic viability of the new sorbent based redox process to convert CO2 into synthesis gas by demonstrating continuous carbon dioxide reduction in a prototype test system for over 585 hours while converting up to 10 kg CO2/day. With the successful completion of the R&D effort, the technology is now ready for a larger pilot-scale demonstration and the technology readiness has been raised from TRL 3 to TRL 5. In collaboration with UCI, we completed a high-fidelity process design and economic analysis. The required sale price (RSP) for gasoline (Case 1 NG-MTG) is $4.91/gal and naphtha and diesel (Case 2 NG-FT) are $4.23/gal and $6.07/gal, respectively, on a 2011 dollar basis. To put these costs in perspective, the California prices in current dollars (with its strict specifications) for regular grade gasoline from last year to current year have varied from a low of $3.10/gal in January 2021 to a high of $5.76/gal in March 2022, while prices for diesel from last year to current year have varied from a low of $3.40/gal in January 2021 to a high of $6.41/gal in May 2022 according to the U.S. Energy Information Agency data. It should be noted that the gasoline and diesel produced by these designs of Case 1 and Case 2 would be of very high quality and both nitrogen and sulfur free. These RSPs are based on a cost of imported electricity of $64/MWh based on the low-end current wind generated electricity cost (Genevieve 2011). This cost is by far the largest component of the variable costs used in computing the RSPs. A sensitivity analysis of these RSPs to the cost of imported electricity shows that the cost of the imported electricity has a significant effect on the RSPs. The life cycle analysis (LCA) shows that the total cradle-to-gate CO2 emissions for both liquid fuels (diesel and gasoline) were negative, indicating that overall more CO2 is consumed than released during production of the fuel from CO2 feed stack for both cases (-296 kgCO2 per MT gasoline for Case 1 and -705 kgCO2 per MT diesel for Case 2). On a cradle-to-grave comparison, the use of diesel produced using TDA’s process (2,457 kgCO2 per MT diesel) would release 37.6% less CO2 compared to petroleum based diesel (3,937 kgCO2 per MT diesel) while the use of gasoline produced using TDA’s process (2,792 kgCO2 per MT gasoline) would release 29.3% less CO2 compared to petroleum based gasoline (3,946 kgCO2 per MT gasoline). With the successful completion of the R&D effort, the technology is now ready for a bench-scale demonstration and the technology readiness has been raised from TRL 3 (Analytical and experimental critical function and/or characteristic proof of concept) to TRL 5 (Laboratory scale similar system validation in relevant environment).

20 FOSSIL-FUELED POWER PLANTS↗

Nuclear Data for Spallation Neutron Radioisotope Production (Final Technical Report)

Over 50 million nuclear medicine procedures are performed annually, leading to a multi-billion dollar market for radioisotope production. The demand for new medical and research isotopes is growing, and radioisotope supply is insufficient. Most radioisotope production today utilizes charged particle or low-energy neutron irradiation of a target. Isotope production with tens to hundred MeV incident energies is a relatively unexplored option. There is a tremendous opportunity associated with a growing number of suitable domestic and international facilities buttressed by hundred million dollar global investments (e.g., the Los Alamos and Brookhaven Isotope Production Facilities, the European Spallation Source in Lund, and the Korean Multi-purpose Accelerator Complex in Gyeongbuk). In part due to a lack of supporting nuclear data that would make modeling radioisotope yields and purities possible, these facilities do not utilize their high-energy neutron fluxes for isotope production. This project attempted to measure neutron reaction excitation functions relevant to the large-scale production of critical radioisotopes, enabling development of cost-efficient isotope production methods, contributing to the improvement of theoretical models, and enhancing the value of national isotope production facilities. Reactions which form 67 Cu, 32 Si, and alpha-emitting isotopes like 225 Ac were chosen for their consistent prioritization by expert panels, representation of diverse reaction mechanisms, and relative lack of supporting nuclear data. Accurate measurement of these data is presently made only using quasi-monoenergetic neutron beams, which are produced by bombarding thin lithium targets with protons at only a few laboratories in the world. Ultimately, the projects efforts were incompletely accomplished due to a combination of multi-year technical issues at the only laboratory in the world which can make the proposed measurements, iThemba Labs in South Africa, and the onset of a global pandemic, which precluded the significant effort and time required to develop an independent measurement capability in the United States.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗