FINAL SCIENTIFIC REPORT– SBIR Phase II THERMAplus, Tunable TES for Different Applications and Climate Zones
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25 ENERGY STORAGE↗
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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Hydrogel-Salt Hydrate Composite for Highly Stable Heat Energy Storage with Reduced Supercooling
Phase change materials (PCM) have potential for use in thermal energy storage in buildings, medical devices, and water heat pumps. Sodium sulfate hydrate (SSD) is appealing due to its high energy storage capability and affordability. However, SSD has issues including high supercooling (> 15°C) and low thermal cyclic stability. In this study, we introduced an ionic molecular nucleating agent that decreases the supercooling temperature to under 2°C. When this SSD was combined with a hydrogel, it maintained its thermal energy storage capacity for over 100 cycles without any decline. The success is attributed to the polymer confining the SSD crystals, preventing large-scale phase separation and the nucleating agent which resulted in nucleation of many small SSD crystals at small undercoolings rather than a small number of larger crystals. As a proof-of-application, we synthesized this composite at a kg scale and demonstrated its properties in a close to real-world demonstration.
chemical composition, thermodynamics↗
Mesolytic cleavage of homobenzylic ethers for programmable end-of-life function in redoxmers
Irreparable chemical damage to redox-active monomers, oligomers, and polymers (i.e. redoxmers) limits the lifetime of energy storage devices (e.g. redox flow batteries) by causing electrode and membrane fouling, as well as irreversible capacity loss. To predictably restore device and materials performance, it is desirable to add programmed destruction capabilities into these damage-prone materials. Here, we report the use of triggerable retrograde reactions to achieve programmable end-of-life function in redoxmers. Retrograde reactions are intended to break up damaged redoxmer materials into more soluble small-molecule constituents to prevent irreparably fouling battery interfaces. We investigated the redox-triggered mesolytic cleavage of homobenzylic ethers (HBEs) for this purpose. Combining experimental methods with simulations, we probed the influence of ring substituents on the programmable bond-scission behavior of HBEs. Variation of para-substituents on the HBEs allowed us to modify the oxidation potential, degradation pathway, and electrochemical mechanisms of the generated products. Given its ideal oxidation potential, we selected the para-methoxy-based HBE as the cleavage scaffold and integrated it with dialkoxybenzene, TEMPO, viologen, and para-nitrobenzene redox centers for compatibility, bulk deconstruction, and electrode defouling tests. Upon applying a high oxidation potential, the redox-active pendant is cleaved from the backbone via HBE bonds; of the four redox centers tested, three of them remained fully redox active. Viologen-appended redox active polymers with HBE linkers were cleaved to fully separate the redox centers from the backbone. Polymer-filmed electrodes were partially restored following HBE oxidation defouling. Here these studies highlight the co-design of new materials functions for developing sustainable energy storage materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
On Energy Storage Chemistry of Aqueous Zn-Ion Batteries: From Cathode to Anode
Rechargeable aqueous zinc-ion batteries (ZIBs) have resurged in large-scale energy storage applications due to their intrinsic safety, affordability, competitive electrochemical performance, and environmental friendliness. Extensive efforts have been devoted to exploring high-performance cathodes and stable anodes. However, many fundamental issues still hinder the development of aqueous ZIBs. Here, we critically review and assess the energy storage chemistries of aqueous ZIBs for both cathodes and anodes. First, this review presents a comprehensive understanding of the cathode charge storage chemistry, probes the existing deficiencies in mechanism verification, and analyzes contradictions between the experimental results and proposed mechanisms. Then, a detailed summary of the representative cathode materials and corresponding comparative discussion is provided with typical cases encompassing structural features, electrochemical properties, existing drawbacks, and feasible remedies. Subsequently, the fundamental chemical properties, remaining challenges, and improvement strategies of both Zn metal and non-Zn anodes are presented to thoroughly explore the energy storage chemistry of ZIBs and pursue the development of high-performance ZIBs. Furthermore, the progress of mechanistic characterization techniques and theoretical simulation methods used for ZIBs is timely reviewed. Finally, here we provide our perspectives, critical analysis, and insights on the remaining challenges and future directions for development of aqueous ZIBs.
25 ENERGY STORAGE↗
Improving charge transport in integrated MoO 3 /C electrode materials for water-in-salt energy storage systems by incorporating oxygen vacancies
Improvements in the charge storage properties of α-MoO 3 used as an electrode with a 30m ZnCl 2 water-in-salt electrolyte have been achieved by enhancements in electron and ion transport enabled by an inventive synthesis route. Electron transport was improved through the integration of MoO 3 with dopamine-derived carbon via a chemical preintercalation route, and enhanced ion transport was achieved by incorporating oxygen vacancies in MoO 3 structure through ethanol 2 reduction under hydrothermal conditions. Here, the presence of carbon was confirmed by corresponding D and G bands observed in Raman spectroscopy measurements. The presence of oxygen vacancies was proven through correlated XPS, TGA, Raman spectroscopy and XRD analyses, with the introduction of oxygen vacancies leading to an expanded interlayer region. Four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon, and cyclic voltammetry-based charge storage mechanism analyses revealed increases in ion transport kinetics due to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. This work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Viability of Additively Manufactured Electrodes for Lithium-Ion Batteries
As the global economy becomes increasingly electrified, the demand for batteries and energy storage is expected to rise significantly, particularly in the transportation and electricity sectors. Lithium-ion batteries (LIBs) are currently the most advanced and widely used technology in this field. Traditionally, LIBs are manufactured using simple 2D planar geometries to maximize production efficiency and minimize costs. However, this approach limits energy density due to the restricted design flexibility of the electrodes. Additive manufacturing (AM) offers a promising solution to enhance the energy density and efficiency of LIBs by enabling the design of architectures that reduce diffusive losses and allow for a greater amount of active material to be incorporated within the same device footprint, thereby minimizing the use of inactive materials. Different AM techniques come with their own set of limitations, including printing speed, material compatibility, and scale, which must be considered when designing electrodes. Scalable and cost-effective methods are particularly important for electric vehicle batteries, while achieving higher energy densities in microbatteries is crucial for the miniaturization of wearable electronics and medical devices. Here, in this study, we simulate various 3D porous electrode designs for LIBs using graphite and nickel manganese cobalt oxide (NMC) electrodes. These designs are selected to represent structures that could be produced using different AM techniques, such as direct ink writing, fused deposition modeling, and stereolithography. Our results indicate that at higher charging rates and increased areal mass loading, 3D structures can outperform traditional 2D electrodes, although the benefits may diminish with more complex designs that are harder to manufacture. The observed gains in energy density are attributed to improved electrode utilization and reduced diffusive energy losses. This comprehensive analysis of structure–performance relationships will provide valuable insights to guide future research on 3D designs, material selection, and AM techniques for additively manufactured battery electrodes.
25 ENERGY STORAGE↗
Fabrication of New PCM Hydrogel Composites
Salt hydrates are low-cost phase-change materials (PCMs) with excellent thermal energy storage capacities. However, they are limited by low thermal cycling stability due to incongruent melting-induced phase separation. This project will solve the long-standing issue of phase separation of salt hydrates by stabilizing salt particles in a charged polymer hydrogel network. The proposed approach uses combined physical and chemical stabilization mechanisms achieved by selecting a proper chemistry and molecular weight of the polymer matrix. In summary, we have identified several important formulations that show good energy storage capacity performance and good cycling stability. The thermal storage capacity can be further improved through further sample optimization. The thermal conductivities of the samples were low, but there are ways to improve it by adding a highly thermally conductive material with a high aspect ratio. The method of preparation is suitable for scale-up.
25 ENERGY STORAGE↗
Technology Strategy Assessment: Findings from Storage Innovations 2030 Thermal Energy Storage
The concept of thermal energy storage (TES) can be traced back to early 19th century, with the invention of the ice box to prevent butter from melting. Modern TES development began with building heating and cooling and concentrated solar thermal technologies for power generation in the early 1900s and late 1970s, respectively. TES systems provide many advantages compared with other long-duration energy storage (LDES) technologies, which include low costs, long operational lives, high energy density, synchronous power generation capability with inertia that inherently stabilizes the grid, and the ability to output both heat and electricity. TES Use Cases TES technologies can couple with most renewable energy systems, including wind, photovoltaic, and concentrated solar thermal energy, and can be used for heat-to-heat, heat-to-electricity, electricity-to-heat, and electricity-to-electricity (bidirectional electricity) applications. The three types of TES that have heat as an input or output are grouped together for the purposes of this report. Retrofitting retired thermal power plants can be a potential cost-effective option for TES with electricity output because they both use a similar thermal-to-electricity type of conversion. Additionally, TES can directly serve heat demand for buildings and industrial processes, displacing fossil fuels to achieve broad decarbonization. Bidirectional Electricity Figure 1 shows a bidirectional electricity TES (ETES) architecture that is emerging as a prime technology for LDES at a grid scale. The ETES technology can utilize existing TES technology infrastructures, has no geological limitations (such as mountains and water for pumped storage hydro, underground natural caverns for compressed-air energy storage, etc.), and is capable of deployment anywhere in the United States and the world for broad uses. Particularly, ETES technology can be placed at retired fossil-fueled thermal power plants to reuse decommissioned assets, protect job security in associated communities, and provide resilient and high-inertia (i.e., spinning) power to the grid. Heat Input and Output There also are many ways to integrate TES within heat-to-electricity, heat-to-heat, and electricity-to-heat applications, such as those used in concentrating solar power (CSP), buildings, district heating, and industry process heat applications. These categories can be further classified for low- and high-temperature applications. High-temperature thermal energy storage (HTTES) heat-to-electricity TES applications are currently associated with CSP deployments for power generation. TES with CSP has been deployed in the Southwestern United States with rich solar resources and has proved its value to the electric grid. Electricity-to-heat and heat-to-heat HTTES applications present great potential for decarbonizing energy-intensive industrial process heat applications [8, 9], such as iron ore processing, iron smelting, cement production, glass manufacturing, mineral processing, and chemical production. Some industrial processes require process heat at temperatures > 1,400°C, so HTTES can be utilized to reduce fuel consumption in those processes through fuel, oxidizer, and process material pre-heating. Thermal energy storage for augmenting existing industrial process heat applications makes a much more attractive economic case because the energy penalty due to thermal-to-electric conversion is eliminated. Co-located applications of power production and heat also can add to the value stacking of integrating utility-scale TES; however, these scenarios are very case specific and not practically possible in many cases. These constraints are primarily attributed to the existing infrastructure being designed, developed, and constructed for many decades around the most economically feasible technologies, such as electricity and a selection of fossil fuels for heat input. Low-temperature TES can be utilized for building and district heating and cooling, as well as some process heat applications in electricity-to-heat and heat-to-heat configurations. Lower temperature TES (LTTES) can be added to heat pump equipment (electric input), either directly interacting with the refrigerant in the condenser or evaporator, or through a secondary heat transfer fluid. It also can be integrated in the building envelope or within the ducts of the heating, ventilation, and air conditioning (HVAC) system. Cost-effective integration of TES into buildings adds significant cost, and it is one of the key barriers preventing the commercialization and deployment of TES. The optimal strategy for integrating TES with buildings has yet to be determined for various applications of TES. Nevertheless, thermal storage materials are far less costly per unit of energy stored than electricity storage materials. This means that thermal storage has the potential to reduce the cost to society of energy storage.
25 ENERGY STORAGE↗
Hydrogen R&D at NREL
This presentation provides an overview of the hydrogen R&D activities at NREL, including make, store, move, and use hydrogen. At NREL, our research spans the advanced water splitting materials (AWSM) and hydrogen storage R&D, performed within the HydroGEN and HyMARC Energy Materials Networks (EMN), respectively, to the materials integration and scale up work done within the H2NEW consortium, to fuel cell R&D within the M2FCT consortium, to stack and systems testing at the MW-level. These R&D activities are funded by U.S. Department of Energy Hydrogen and Fuel Cell Technologies Office.
08 HYDROGEN↗
Leveraging metal hydrides for strategic thermal energy control
Attributes of Sensible Heat Materials • Typically based on highly abundant and lowcost materials • Store thermal energy based on the heat capacity (or specific heat) of the material • Duration of thermal energy storage depends on how well the system is insulated • Has the lowest thermal energy storage density • Can be pumped as a fluid Attributes of Latent Heat Materials • Also based on highly abundant materials, but typically cost slightly more than sensible heat materials • Store thermal energy based on the heat of the phase change (i.e., heat of fusion) and the specific heat of the material • Duration of thermal energy storage depends on how well the system is insulated • Has a higher thermal energy storage density than sensible heat materials, but cannot be pumped as a fluid
WARD, PATRICK↗
Dielectric polymers for high-temperature capacitive energy storage
Polymers are the preferred materials for dielectrics in high-energy-density capacitors. The electrification of transport and growing demand for advanced electronics require polymer dielectrics capable of operating efficiently at high temperatures. In this review, we critically analyze the most recent development in the dielectric polymers for high-temperature capacitive energy storage applications. While general design considerations are discussed, emphasis is placed on the elucidation of the structural dependence of the high-field dielectric and electrical properties and the capacitive performance, including discharged energy density, charge–discharge efficiency and cyclability, of dielectric polymers at high temperatures. Here, advantages and limitations of current approaches to high-temperature dielectric polymers are summarized. Challenges along with future research opportunities are highlighted at the end of this article.
25 ENERGY STORAGE↗
Simultaneous Electrospinning and Electrospraying for the Preparation of a Precursor Membrane Containing Hydrothermally Generated Biochar Particles to Produce the Value-Added Product of Carbon Nanofibrous Felt
Biochar is a byproduct generated from the hydrothermal liquefaction of biomass, such as corn stover, in an anaerobic environment. This work aims to convert biochar into a value-added product of carbon nanofibrous felt. First, the biochar-containing precursor membrane was prepared from simultaneous electrospinning and electrospraying. After thermal stabilization in air and carbonization in argon, the obtained precursor membrane was converted into a mechanically flexible and robust carbon nanofibrous felt. Electrochemical results revealed that the biochar-derived carbon nanofibrous felt might be a good candidate as a supercapacitor electrode with a good rate capability and high kinetic performance.
25 ENERGY STORAGE↗
Experimental Analysis of Salt Hydrate Latent Heat Thermal Energy Storage System With Porous Aluminum Fabric and Salt Hydrate as Phase Change Material With Enhanced Stability and Supercooling
Phase change materials (PCMs), especially salt hydrates possess high volumetric energy storage capacity in their transition temperature range. These materials are used in applications where it is necessary to store thermal energy due to temporary load shift between demand and availability. Thus, possible applications are HVAC, recovery of waste heat, and defense thermal management. Despite salt hydrates potential, the practical feasibility of latent heat storage with salt hydrates is limited due to low power rating, supercooling, phase segregation, and long-term stability. Its low power rating and long-term stability limits its application in most applications. This work experimentally validates the stability and thermal performance of a compact heat exchanger charged with salt hydrate during melting and freezing. The compact heat exchanger was designed with fins on both the heat transfer fluid (HTF) and salt hydrate PCM side. The thermal performance of the latent heat thermal energy storage system (LHTESS) was evaluated for various operating conditions. The results show that LHTESS could achieve an average heat transfer coefficient of 124 and 87 W/(m2 K) during melting and solidification, respectively. The stability of the system in suppressing supercooling was validated over 800 cycles with nucleating agent and active homogenous nucleation techniques. The supercooling was reduced to 3 °C with zinc hydroxyl nitrate as nucleating agent and less than 1 °C with the active homogenous nucleation technique. The LHTESS showed less than 6% degradation in energy storage capacity over 800 cycles.
42 ENGINEERING↗
Rechargeable alkaline battery using organic materials as negative electrodes
An energy storage device may provide a positive electrode, an electrolyte, and a negative electrode. The energy storage device may utilize an aqueous alkaline electrolyte, which may be nonflammable. The energy storage device may utilize organic material(s) as the negative electrode, such as, but not limited to, poly(anthraquinonyl sulfide) (PAQS), organic carbonyl compounds, organosulfur compounds, redox polymers, or radical polymers.
25 ENERGY STORAGE↗
Machine-learning-assisted deciphering of microstructural effects on ionic transport in composite materials: A case study of Li 7 La 3 Zr 2 O 12 -LiCoO 2
The effective diffusivity of ionic species in multiphase materials is critical for the design and function of composite materials for electrochemical energy storage. In practice, effective diffusivity depends sensitively not only on the intrinsic diffusivities of constituting materials but also on their topological arrangement; nevertheless, these coupled contributions are oversimplified in most analytical models. Here, we combine atomistically informed mesoscale modeling and machine learning (ML) analysis to unravel how such features affect effective diffusivity in two-phase composites. Using the Li 7 La 3 Zr 2 O 12 -LiCoO 2 composite solid-state battery cathode as a model system, we compute effective diffusivity for 600 distinct dense polycrystalline microstructures with different topological configurations of grains, grain boundaries, and heterointerfaces. We verify that in addition to atomic-scale variabilities, microstructural feature diversity can significantly impact effective transport properties. Across the ensemble of test microstructures, this often results in bimodal distributions of effective diffusivity that encompass two qualitatively distinct operating mechanisms, which we identify via flux analysis. An ML approach reveals that the most critical determining factors for effective diffusivity are the connectivity of bulk phases and their heterointerfaces. The role of ionic mobility at the heterointerfaces is also discussed. These insights highlight the combined importance of microstructure and interface engineering in tuning the transport properties of ionic species in composite materials. In conclusion, our framework can also be extended for understanding generic microstructure-property relationships in other complex multiphase materials.
25 ENERGY STORAGE↗
Nature-inspired lotus-shaped fins combined with hybrid nanoparticles and metal foam for high-performance latent heat thermal energy storage
Latent heat thermal energy storage (LHTES) systems play a critical role in renewable energy integration by providing high energy density and nearly isothermal operation during phase transitions. However, their performance is often limited by slow melting/charging rates, which motivates the search for enhanced heat transfer designs. This study investigates the melting behavior of RT-82 phase change material (PCM) using novel lotus-shaped fins combined with copper metal foam and conductive graphene nanoparticles and carbon nanotubes. A two-dimensional enthalpy-porosity model in ANSYS Fluent was developed to simulate the charging/melting process, capturing non-thermal equilibrium between the foam and PCM/nano-PCM. In this study, effects of fin geometry, nanoparticle concentration, and foam porosity on melting dynamics and cost-performance trade-offs were investigated. Results showed that natural convection accelerated melting by ~12% compared to conduction-only scenarios. Optimized lotus-shaped fins with higher fin density (T3F4 and T3F10) achieved up to 63% faster melting relative to sparse configurations. Graphene nanoparticles improved thermal conductivity, with a 6% volume fraction, by reducing melting time by ~6.9%, while their combination with 75% porosity foam achieved a maximum reduction in the melting time of ~51% compared to pure PCM. Cost-performance analysis identified T3F4 as the most balanced design, offering rapid thermal response without excessive material costs, while moderate-density designs like T3S6 provided economical alternatives with acceptable performance. These results highlight the performance enhancement that can be achieved by integrating bio-inspired fins, nanoparticles, and foams, into compact and efficient LHTES for solar heating, building thermal management, and industrial waste-heat recovery applications.
25 ENERGY STORAGE↗
Hydrogen-Bonding Reinforced Flexible Composite Electrodes for Enhanced Energy Storage
The lack of advanced electrode materials is one of the main factors hindering the development of flexible rechargeable aqueous batteries (RABs) for high specific energy density and structural stability. It is also challenging to achieve high-capacity performance for both the positive and negative electrodes simultaneously. In this work, it is demonstrated that, by smartly designing the composite structures of positive and negative electrodes via one-step electrodeposition strategy, the energy storage performance of the RAB is largely enhanced. For positive electrode material synthesis, Co-Cu double hydroxides (Co-Cu-DH) nanosheets are skillfully rooted into electroreduced graphene oxide (eRG) via hydrogen bonding, in which graphene oxide reduction, Co-Cu-DH nucleation/growth, and formation of hydrogen bonding between Co-Cu-DH and eRG simultaneously occur. Moreover, when a RAB based on Co-Cu-DH@eRG//FeOOH@eRG using the same composite design strategy is established, a wide operating voltage window of ≈1.8 V, a high specific energy density of ≈142.8 Wh kg –1 at ≈890 W kg –1 , and long-term cyclic stability (88.5% of capacity retention after 12 000 cycles) are obtained. This study presents a general compositing strategy for the development of advanced electrode materials, and it is expected to stimulate future material synthesis/design in RABs toward the goal of high energy density storage.
25 ENERGY STORAGE↗