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SpecFIDLER User Manual (Software V.2.3.0)

The Spectroscopic Field Instrument for Detection of Low Energy Radiation (SpecFIDLER) allows response teams to detect and quantify plutonium contamination on the ground. Notional scenarios include dispersion from a weapon accident, or the launch failure of a space probe containing a radioisotope thermoelectric generator. Unlike other instruments, the thin-window sodium iodide detector is sensitive to the low-energy gamma rays emitted by plutonium isotopes. The system supports both mobile survey as well as stationary sampling. This manual provides information about installing, maintaining, and troubleshooting the SpecFIDLER. The scope of this document includes the physical hardware, software for data acquisition, and algorithms for data analysis. Recent changes to the software and algorithms aim to streamline the operation of the system.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

NASA Dragonfly Mission MMRTG

The Radioisotope Power Systems (RPS) group at the Idaho National Laboratory (INL) is supporting NASA’s New Frontier class mission, Dragonfly, to explore the Saturn moon Titan. Titan has been observed by both Voyager spacecrafts in 1979 and 1980 and during over 100 close flyby encounters by the Cassini orbiter and subsequent landing of the Huygens probe which landed on Titan in 2005. The probe lasted about 2.5 hours without an RPS due to the thick atmosphere and cold climate but gave scientists valuable insight into the geology of Titan. The surface is composed of vast sand dunes and liquid methane with an atmosphere composed primarily of nitrogen that is 60% more dense as the Earth’s with 1/7th of Earth’s gravity. These conditions allow for exploration using a dual-quadcopter. Due to the extreme temperatures (-290°F or -180°C), changes to the Multi-Mission Radioisotope Thermoelectric Generator (MMRTG) are required. This generator, designated flight unit 4 or MMRTG-F4, is being built by a team lead by INL and includes the prime contractor Aerojet Rocketdyne and their supplier Teledyne Energy System. This poster outlines the mission, the unique challenges and updates the build progress.

42 ENGINEERING↗

Chapter 6: Thermoelectric Energy Harvesters and Applications

With recent progress in the field of wearable and bio-integrated devices, which are widely used for various applications, such as real-time health monitoring, point-of-care diagnostics, and biological actuators, the need for a continuous and reliable power source is increasing. As solid-state devices with no moving parts, thermoelectric energy generators provide a reliable solution for harnessing body heat and converting it into electricity on demand. However, traditional thermoelectric generators, comprising inorganic materials, are rigid and bulky, limiting their wide deployment. Nonconventional thermoelectric generators, composed of organic and hybrid thermoelectric materials, are flexible and lightweight. In this chapter, we will discuss the working principle of thermoelectric energy harvesting, including materials, devices, and applications. While we briefly touch upon the inorganic materials, we will focus primarily on the organic and hybrid materials, which are nontoxic, flexible, easy to manufacture, easy to scale, and readily available at low cost, providing a promising solution for lightweight and conformal thermoelectric power generation.

body heat harvesting↗

Ga 4 C-family crystals, a new generation of star thermoelectric materials, achieved by band degeneracies, valley anisotropy, and strong phonon scattering among others

Using density functional theory combined with the Boltzmann transport equation, we uncover a new class of high-performance thermoelectric materials, i.e., supertetrahedral Ga 4 C-family materials characterized by an ultrahigh thermoelectric figure of merit (ZT), which is produced both by a large power factor and ultralow lattice thermal conductivity. The former is contributed by multiple electronic band degeneracies, flat bands and valley anisotropy, while the latter is contributed both by strong phonon scattering and low phonon group velocity. Furthermore, we find that tensile strain engineering may further suppress lattice thermal conductivity, while well retaining the multi-band degeneracies, valley anisotropy and flat bands. In addition to the band degeneracy, the scattering mechanism of the system can also dominate the power factor in the process of strain implementation. Consequently, a novel thermoelectric phenomenon, i.e., a high thermoelectric figure of merit, is observed in Ca 4 C with a ZT value larger than 4.4 under a small strain ratio (0.75%). In conclusion, our theoretical studies not only uncover a new class of high-performance thermoelectric materials integrating multiple effective mechanisms, but also establish a realistic material plateau to investigate the competitive effect of multiple factors on enhancing the thermoelectric figure of merit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Maximal nighttime electrical power generation via optimal radiative cooling

We present a systematic optimization of nighttime thermoelectric power generation system utilizing radiative cooling. We show that an electrical power density >2 W/m 2 , two orders of magnitude higher than the previously reported experimental result, is achievable using existing technologies. This system combines radiative cooling and thermoelectric power generation and operates at night when solar energy harvesting is unavailable. The thermoelectric power generator (TEG) itself covers less than 1 percent of the system footprint area when achieving this optimal power generation, showing economic feasibility. We study the influence of emissivity spectra, thermal convection, thermoelectric figure of merit and the area ratio between the TEG and the radiative cooler on the power generation performance. We optimize the thermal radiation emitter attached to the cold side and propose practical material implementation. The importance of the optimal emitter is elucidated by the gain of 153% in power density compared to regular blackbody emitters.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Printing thermoelectric inks toward next-generation energy and thermal devices

The ability of thermoelectric (TE) materials to convert thermal energy to electricity and vice versa highlights them as a promising candidate for sustainable energy applications. Despite considerable increases in the figure of merit zT of thermoelectric materials in the past two decades, there is still a prominent need to develop scalable synthesis and flexible manufacturing processes to convert high-efficiency materials into high-performance devices. Scalable printing techniques provide a versatile solution to not only fabricate both inorganic and organic TE materials with fine control over the compositions and microstructures, but also manufacture thermoelectric devices with optimized geometric and structural designs that lead to improved efficiency and system-level performances. In this review, we aim to provide a comprehensive framework of printing thermoelectric materials and devices by including recent breakthroughs and relevant discussions on TE materials chemistry, ink formulation, flexible or conformable device design, and processing strategies, with an emphasis on additive manufacturing techniques. Additionally, we review recent innovations in the flexible, conformal, and stretchable device architectures and highlight state-of-the-art applications of these TE devices in energy harvesting and thermal management. Perspectives of emerging research opportunities and future directions are also discussed. While this review centers on thermoelectrics, the fundamental ink chemistry and printing processes possess the potential for applications to a broad range of energy, thermal and electronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water and Climate Impacts on ERCOT Long-Term Systems Assessment

Water and climate change pose many potential challenges to the electric power system. Substantial water is withdrawn every day to support thermoelectric power generating unit operations, and changes to water supply have the potential to affect generation dispatch. Climate change can accelerate growing demand for electricity, which can necessitate additional generating capacity, often in locations with limited water supply. Drought conditions also threaten thermoelectric power plant operations due to streamflow and reservoir levels dropping below intake structures, or water temperatures exceeding a power plants' permitted operating conditions. Here we explore how future climate change might influence decisions related to electricity capacity expansion planning in Electric Reliability Council of Texas (ERCOT) using a multi-model framework. Specifically, water resource modeling is used to simulate climate impacts on the future water supply for thermoelectric and hydropower generation for four future climate projections. Separately, temperature impacts on electricity load are evaluated for these scenarios. These climate impacts are applied to five alternative electricity futures in an electricity capacity expansion model that projects future generation and transmission capacity additions in ERCOT. Results indicate that climate has a measurable influence on future generation and transmission capacity needs, with temperature-driven increases in peak and average load resulting in 5-15 GW additional generating capacity and up to 1 GW additional transmission capacity. Additional capacity is a diverse mix of PV, natural gas, and wind, depending on the makeup of economic, policy and technology assumptions. Climate impacts increase total system costs 2-5%, while the marginal cost of energy and emissions are not affected substantially by climate change effects.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

An International Round-Robin Study on Thermoelectric Module Testing and Development of Standard Power Generation Modules

An international round-robin study on thermoelectric power generation modules was conducted with nine participating laboratories. Two types of commercially available bismuth telluride modules, 30 mm × 30 mm and 40 mm × 40 mm, were used. A test protocol was followed with five temperature set points from 50°C to 150°C. Graphite sheets were used as thermal interface materials with test pressure at 100 psi (0.69 MPa). The results showed large lab-to-lab variations and the key source of uncertainty for module efficiency was identified as the heat flux measurement. In the meantime, significant uncertainty was also found in maximum electrical power (P max ) measurements. As a result of the round-robin, a “standard module” with 4 × 4 legs on a 20 mm × 20 mm platform was suggested. A skutterudite module and a half-Heusler module were produced with identical geometry and 4 mm × 4 mm × 8 mm legs. All transport properties to calculate the figure-of-merit, zT, were measured from ambient temperature to 500°C. Module performance was measured by two laboratories. Two finite-element-analysis (FEA)-based models were developed independently to simulate and predict the module performance. In conclusion, the standard modules eliminated significant test uncertainties and are aimed at assisting device design and achieving more accurate performance predictions.

Round-robin↗

ZrCoBi based half Heuslers with high thermoelectric conversion efficiency

A method of thermoelectric power generation by converting heat to electricity via the use of a ZrCoBi-based thermoelectric material, wherein a thermoelectric conversion efficiency of the ZrCoBi-based thermoelectric material is greater than or equal to 7% at a temperature difference of up to 800 K.

Ren, Zhifeng↗

Toward High Conversion Efficiency of Thermoelectric Modules through Synergistical Optimization of Layered Materials

Abstract Waste‐heat electricity generation using high‐efficiency solid‐state conversion technology can significantly decrease dependence on fossil fuels. Here, a synergistical optimization of layered half‐Heusler (hH) materials and module to improve thermoelectric conversion efficiency is reported. This is realized by manufacturing multiple thermoelectric materials with major compositional variations and temperature‐gradient‐coupled carrier distribution by one‐step spark plasma sintering. This strategy provides a solution to overcome the intrinsic concomitants of the conventional segmented architecture that only considers the matching of the figure of merit ( zT ) with the temperature gradient. The current design is dedicated to temperature‐gradient‐coupled resistivity and compatibility matching, optimum zT matching, and reducing contact resistance sources. By enhancing the quality factor of the materials by Sb‐vapor‐pressure‐induced annealing, a superior zT of 1.47 at 973 K is achieved for (Nb, Hf)FeSb hH alloys. Along with the low‐temperature high‐ zT hH alloys of (Nb, Ta, Ti, V)FeSb, the single stage layered hH modules are developed with efficiencies of ≈15.2% and ≈13.5% for the single‐leg and unicouple thermoelectric modules, respectively, under Δ T of 670 K. Therefore, this work has a transformative impact on the design and development of next‐generation thermoelectric generators for any thermoelectric material families.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

River Regulation Alleviates the Impacts of Climate Change on US Thermoelectricity Production

Climate change and anthropogenic activities can both influence stream temperature, which is a critical indicator of thermoelectric power generation potential. Previous studies emphasized the vulnerability of power-generation systems to climate warming (ref 1, 2). Despite the fact that two-thirds of the global rivers are regulated by dams (ref 3), the relative impacts of water management and climate change on stream temperature and thermoelectric production have not yet been evaluated. Using an integrated modeling system applied to the conterminous United States, simulations confirm the dominant role of climate change in shaping the future trends of stream temperature. However, water management, reservoir regulation in particular, can mitigate the stream temperature warming and reduce the frequency and magnitude of extreme high stream temperatures through redistribution of the seasonal streamflow. Moreover, water management can alleviate the loss of power plant usable capacity from climate change to the level of reduced warming from emission mitigation. By regulating the flow and temperature regimes, water management is a promising adaptation measure to alleviate climate change induced effects in the water-energy nexus.

Zhang, Xiao↗

Polycrystalline SnSe with a thermoelectric figure of merit greater than the single crystal

Abstract Thermoelectric materials generate electric energy from waste heat, with conversion efficiency governed by the dimensionless figure of merit, ZT. Single-crystal tin selenide (SnSe) was discovered to exhibit a high ZT of roughly 2.2–2.6 at 913 K, but more practical and deployable polycrystal versions of the same compound suffer from much poorer overall ZT, thereby thwarting prospects for cost-effective lead-free thermoelectrics. The poor polycrystal bulk performance is attributed to traces of tin oxides covering the surface of SnSe powders, which increases thermal conductivity, reduces electrical conductivity and thereby reduces ZT. Here, we report that hole-doped SnSe polycrystalline samples with reagents carefully purified and tin oxides removed exhibit an ZT of roughly 3.1 at 783 K. Its lattice thermal conductivity is ultralow at roughly 0.07 W m –1 K –1 at 783 K, lower than the single crystals. The path to ultrahigh thermoelectric performance in polycrystalline samples is the proper removal of the deleterious thermally conductive oxides from the surface of SnSe grains. These results could open an era of high-performance practical thermoelectrics from this high-performance material.

36 MATERIALS SCIENCE↗

Evolution of Dissipative Regimes in Atomically Thin Bi 2 Sr 2 CaCu 2 O 8 + x Superconductor

Thermoelectric transport is widely used to study Abrikosov vortex dynamics in unconventional superconductors. However, only a few thermoelectric studies have been conducted near the dimensional crossover that occurs when the vortex-vortex interaction length scale becomes comparable to the sample size. Here, the effects of finite size on the dissipation mechanisms of the Nernst effect in the optimally doped Bi 2 Sr 2 CaCu 2 O 8 + x high-temperature superconductor are reported, down to the atomic length limit. To access this regime, a new generation of thermoelectric chips based on silicon nitride microprinted circuit boards is developed. These chips ensure optimized signals while preventing sample deterioration. The results demonstrate that lateral confinement at the nanoscale can effectively reduce vortex dissipation. Investigating vortex dissipation at the micro- and nano-scale is essential for creating stable, miniaturized superconducting circuits.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Solution-phase p-type doping of highly enriched semiconducting single-walled carbon nanotubes for thermoelectric thin films

Single-walled carbon nanotubes (SWCNTs) are attractive materials for next-generation energy-harvesting technologies, including thermoelectric generators, due to their tunable opto-electronic properties and high charge carrier mobilities. Controlling the Fermi level within these unique 1D nanomaterials is often afforded by charge transfer interactions between SWCNTs and electron or hole accepting species. Conventional methods to dope SWCNT networks typically involve the diffusion of molecular redox dopant species into solid-state thin films, but solution-phase doping could potentially provide routes and/or benefits for charge carrier transport, scalability, and stability. Here, we develop a methodology for solution-phase doping of polymer-wrapped, highly enriched semiconducting SWCNTs using a p-type charge transfer dopant, F4TCNQ. This allows doped SWCNT inks to be cast into thin films without the need for additional post-deposition doping treatments. We demonstrate that the introduction of the dopant at varying stages of the SWCNT dispersion process impacts the ultimate thermoelectric performance and observe that the dopant alters the polymer selectivity for semiconducting vs metallic SWCNTs. In contrast to dense semiconducting polymer films, where solution-phase doping typically leads to disrupted morphologies and poorer TE performance than solid-state doping, thin films of solution-doped s-SWCNTs perform similarly to their solid-state doped counterparts. Interestingly, our results also suggest that solution-phase F4TCNQ doping leads to fully ionized and dimerized F4TCNQ anions in solid-state films that are not observed in films doped with F4TCNQ after deposition. Our results provide a framework for the application of solution-phase doping to a broad array of high-performance SWCNT-based thermoelectric materials and devices that may require high-throughput deposition techniques.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Morphological Ordering of the Organic Layer for High-Performance Hybrid Thermoelectrics

Inorganic-organic hybrids, such as Te-PEDOT:PSS core/shell nanowires, have emerged as a class of promising thermoelectric materials with combined attributes of mechanical flexibility and low cost. However, the poorly understood structure-property relationship calls for further investigation for performance enhancement. Here, through precise treatments of focused electron beam irradiation and thermal annealing on individual Te-PEDOT:PSS nanowires, new, nonchemical mechanisms are introduced to specifically engineer the organic phase, and the measured results provide an unprecedented piece of evidence, confirming the dominant role of organic shell in charge transport. Paired with the Kang-Snyder model and molecular dynamics simulations, this work provides mechanistic insights in terms of heating-enabled morphological ordering of the polymer chains. The measured results show that thermal annealing on the 42 nm nanowire results in a ZT value of 0.78 at 450 K. In conclusion, through leveraging the interfacial self-assembly of the organic phase to construct a high electrical conductivity domain, this work lays out a clear framework for the development of next-generation soft thermoelectrics.

36 MATERIALS SCIENCE↗

Review of the General-Purpose Heat Source Module Reduction and Monitoring Processing at INL

A thorough review of the Module Reduction and Monitoring (MRM) process was conducted to evaluate the efficacy of processing. The degree of reduction was calculated using the mass balance of oxygen contained in carbon monoxide (CO) and carbon dioxide (CO 2 ) removed from all fuel processed between January 2014 through August 2019. The plutonia was slightly reduced from O/Pu ratio of 2.0 to a range of 1.991 to 1.999. The review evaluated publications generated when MRM processing was developed and performed at the Mound Laboratory. A similar degree of reduction was measured at Mound in the 1982 paper authored by Ernie Johnson as well as MRM processing of IHS-60 and some Cassini-era fuel. The original 1982 paper documenting the reduction process reported a mass balance reduction to 1.9931 yet reported a total reduction to ~1.98 (Johnson 1990). The IHS-60 and Cassini reductions were calculated at 1.995 and 1.997 using the number of moles of CO and CO 2 removed as published in a clad pressurization investigation report (Merten, et all 1995). MRM process changes are recommended to improve the accuracy of the CO partial pressure calcualtion.

42 ENGINEERING↗

A heat flux sensor leveraging the transverse Seebeck effect in elemental antimony

Certain configurations of anisotropic single crystal materials can generate a thermoelectric voltage orthogonal to an induced temperature gradient. This phenomenon is known as the Transverse Seebeck Effect (TSE) and can be leveraged to fabricate simple and robust heat flux sensors. Only a small number of materials have been considered as TSE-based transducers and, among these, few have been developed into sensors with ruggedization against chemical and mechanical degradation. Here, we report on the fabrication and characterization of a rugged TSE-based heat flux sensor using prismatic antimony single crystals. The heat flux sensor was tested under static and dynamic heating scenarios. The sensor has a linear responsivity of 16.8 µV/(W/cm2) to heat fluxes spanning more than two orders of magnitude and a time constant of 4.4 s. The sensor’s response to localized heating, probed with a laser scanning technique, validated that the transduction mechanism is primarily the TSE by ruling out a sizable contribution from the conventional Seebeck effect. Finite element analysis corroborated that components used in the sensor package are the primary determinants of the time constant and the decrement of the responsivity from its theoretical maximum. Design principles that may be applied to elicit a faster transient response or higher responsivity are proposed. Furthermore, the results establish single crystal antimony as a promising transducer material for heat flux measurement systems and demonstrate potential effects of ruggedization on sensor performance.

36 MATERIALS SCIENCE↗

Thermoelectric coatings for waste heat recovery and photo-thermal power

An energy harvesting system for collecting energy from sources of thermal energy that exist in the environment and convert the energy to electricity. The system has N-P junctions mounted on the outer surface of a conduit, pipe or flue. A hot medium flows through the conduit, pipe or flue. The p-n junctions operate as thermoelectric power generators. Heat absorbed at the p-n junctions increases the kinetic energy of charge carriers causing migration of the charge carriers. This thermally-driven migration of charge carriers is used to drive an electrical current in an external circuit.

Farmer, Joseph C.↗