Solar Thermal Energy Storage System Research Articles

Lattice Boltzmann simulation of effects of realistic boundary conditions on volumetric radiation‐conduction melting of a novel cylindrical enclosure filled with phase change materials

AbstractIn this research, a novel solar latent heat thermal energy storage (LHTES) system, including the cylindrical enclosures filled with a phase change material (PCM), is proposed, which can be installed on the building windows to alleviate the drawbacks of traditional PCM‐filled double‐glazed windows, such as daylight hindrance and leakage. The lattice Boltzmann method (LBM) is used to simulate the volumetric radiation‐conduction melting of the PCM within a single cylinder of the proposed LHTES system with considering more realistic conditions such as convective boundary condition, shadow effect, and variable solar radiation angle compared with the available works in the literature. As such, several boundary conditions are assessed, and parameters such as cylinder diameter, extinction coefficient, scattering albedo, solar angle, shadow effect, and natural convection heat transfer coefficient are studied on the time history of the melting fraction and charging time. The results revealed that considering the applied conditions, such as convection heat loss to the environment and shadow, significantly affects the charging time of the system. It is shown that the charging time for convective boundary condition with , , and increases, respectively, by 11%, 30%, and 50% relative to a case with the insulated boundary condition without the shadow effect and 38%, 91%, and 175% compared with the insulated case with a 90° shadow.

Novel route to enhance the thermo-optical performance of bicyclic diene photoswitches for solar thermal batteries.

Harnessing solar energy by employing chemical photoswitches in molecular solar thermal (MOST) energy storage systems is a topic of appealing research interest. However, incorporating all the features desired for an ideal MOST system in a single photoswitching couple is challenging. Inspired by experimental synthesis, herein we report our attempt to enhance both the thermochemical and photophysical properties in a single-bridged bicyclic diene (BBD)-based photoswitch by elongating the unsaturated bridge with different heteroatomic units. To elucidate the best elongation unit, the energy storage capacity and the TBR barriers were accounted using the DLPNO-CCSD(T) and (8,8)-CASPT2 methods, respectively. The photophysical properties including the absorption onset, excitation wavelengths, and the absorption intensities were extensively investigated with the time-dependent calculations. The result provides information on the most versatile solvent to exhibit the best photoswitching behaviour which is beneficial for real-life energy storage applications. Additionally, the stability and reversibility of the photoswitching system with elongated unsaturated bridges have also been assessed. By means of the studied modification, the storage energy of 158.57 kJ/mol, energy storage density of 1.48 MJ/kg, TBR barrier of 136.36 kJ/mol, and the absorption onset of 305.00 nm is achieved in acetonitrile. These values are substantially higher when compared with the storage energy (96.06 kJ/mol), energy storage density (1.04 MJ/kg), and TBR barrier (121.76 kJ/mol) of prototype NBD/QC in the gas phase. The outcomes render useful insights into the stability and properties of bicyclic diene-based photoswitches having elongated unsaturated bridges and indeed paves the way for the rational design of practical MOST systems.

Numerical and three-factor design investigation for melting process of phase-change spherical capsules in a solar thermal energy storage system

The application of spherical phase-change capsules in solar thermal energy storage systems (STESS) can enhance the sustainability and stability of energy output in solar energy utilization, making it a recent research hotspot. Nonetheless, the influence of neglecting three-dimensional effects through structural simplification on the phase-change process and the criteria for selecting the mushy zone constant in numerical studies are still not well-defined. In this context, a detailed analysis is conducted to investigate the variations in liquid fraction, temperature, flow field, and the time required for complete PCM melting caused by the structural simplification method. Subsequently, a three-factor design analysis is performed on parameters including spherical radius (R), mushy zone constant (Amush) and phase-change temperature range (ΔT) with the aim of establishing a rational basis for selecting the mushy zone constant. Results show that the simplification of the 3D spherical encapsulation structure into a two-dimensional (2D) circular encapsulation structure introduces notable discrepancies in the PCM melting process. In contrast to the 2D circular encapsulation structure, the 3D spherical encapsulation structure demonstrates a reduction in the time required for complete PCM melting by 23 % to 36 %. The influence of simplifying the 3D spherical encapsulation structure into a 2D axisymmetric encapsulation configuration on the numerical simulation of the PCM melting process becomes more pronounced with the increase of R. For the 3D spherical encapsulation structure, the hierarchy of significance regarding the factors influencing the PCM melting process manifests in the sequence: R, Amush, (R × Amush), and ΔT. Furthermore, the formulated correlation based on the aforementioned four factors enables precise prediction of the time required for complete PCM melting within the 3D spherical encapsulation structure and offers a foundation for selecting the appropriate Amush value in numerical simulation. The present work contributes novel insights into the accuracy and rationality of numerical simulations for phase-change processes in the STESS.

Polycyclic Heteroaromatic π‐Linkers Provide Dithienylethene Switches with Favorable Thermal and Photochemical Properties for Solar‐Energy Storage

AbstractDithienylethene photoswitches with an aromatic π‐linker as the bridge between the two thiophene units are attractive starting materials for developing molecular solar thermal energy (MOST) storage systems, partly because the aromaticity of their ring‐open forms is a favorable feature with regard to the energy‐storage densities of their ring‐closed forms produced by photoinduced electrocyclization (photocyclization) reactions. At the same time, this typically leads to small barriers for their thermal cycloreversion reactions, which are not desirable in this context. Here, we use computational methods to show that this problem can be circumvented with polycyclic heteroaromatic π‐linkers. Specifically, through the tuning of the aromatic character of the individual rings of such a π‐linker (like indole or isoindole), it is shown to be possible to strike a delicate balance between the seemingly contrasting requirements of simultaneously achieving both a high energy‐storage density and a large cycloreversion barrier. Furthermore, this design is also found to provide for a quick and efficient photocyclization reaction, owing to the onset of excited‐state antiaromaticity in the π‐linker upon light absorption of the ring‐open form. Altogether, dithienylethenes with polycyclic heteroaromatic π‐linkers appear to have both thermal and photochemical properties suitable for further development into future MOST systems.

Visible-Light-Sensitive Photoliquefiable Arylazoisoxazoles for the Solar Energy Conversion, Storage and Controlled-Release of Heat at Room Temperature or Lower Temperatures.

The photoswitchable MOlecular Solar Thermal (MOST) energy storage systems that are capable of exhibiting high energy storage densities are found to suffer from the poor cyclability, the use of less abundant UV light of the solar spectrum, or reduced charging/discharging rates and poor photoconversions in solid states. Herein, we have designed and readily synthesized a novel set of para-thioalkyl substituted arylazoisoxazoles, that undergo high trans-cis and cis-trans photoconversions under visible light, and show fast charging/discharging and impressive cyclability. Remarkably, the presence of C6-or C10-thioalkyl chainin photochromes permitted reversible solid-liquid phase transition with the formation of cis-enriched charged states by 400 nm light irradiation and trans-enriched discharged states by 530 nm light at various temperatures (10-35 °C). The solid-to-liquid phase transition enabled storage of the latent heat in addition to the isomerization energy, resulting in a high net energy storage density of 189-196 J/g, which are substantially higher than that of many recently reported azobenzene-based MOST compounds (100-161 J/g). Using a high-resolution infrared camera, we further demonstrated that a brief irradiation of green light can be employed to readily release the trapped photon energy as heat. Our results suggest that the arylazoisoxazole with C6-thioalkyl chain at para-position can serve as an effective and eco-friendly photoliquefiable MOST material.

Solar Thermal Energy Storage Systems Based on Discotic Nematic Liquid Crystals That Can Efficiently Charge and Discharge below 0 °C

AbstractSolid‐state solar thermal fuels (SSTFs) serve as efficient means of storing solar energy as chemical potential energy in a closed loop system and releasing it as heat on‐demand. An ideal SSTF requires photoswitchability in visible‐region without any external heating as well as extended storage times. However, existing systems often rely on ultraviolet (UV) light or heating for photoswitching, or suffer from low storage times. Addressing this, a novel strategy is presented to obtain visible‐light responsive SSTFs designed to operate effectively at room‐temperature or sub‐zero temperatures by innovatively integrating a tetra‐ortho‐fluoro/chloro azobenzene arm in triphenylene based liquid crystal (LC) moiety. The resulting compounds exhibit discotic nematic (ND) mesophases till −6.5 °C. These compounds exhibit excellent photocyclability, photostability, and sufficient half‐lives of cis states. Achieving up to 77% charging under sunlight with a bandpass filter and 62.4% without it, these systems uniquely demonstrate efficient chargeability and dischargeability at sub‐zero temperatures. Upon discharging, temperature rise of up to 6.5 and 29.5 °C occur at room‐temperature (25 °C) and sub‐zero temperatures (around −6 to −7 °C), respectively. This efficacy is attributed to less‐ordered ND phases providing conformational freedom for photoisomerization at low temperatures.

Synthesis and Characterization of Carbon-Based Heterogeneous Catalysts for Energy Release of Molecular Solar Thermal Energy Storage Materials.

Molecular solar thermal energy storage (MOST) systems are rapidly becoming a feasible alternative to energy storage and net-zero carbon emission heating. MOST systems involve a single photoisomerization pair that incorporates light absorption, storage, and heat release processes in one recurring cycle. Despite significant recent advancements in the field, the catalytic back-reaction from MOST systems remains relatively unexplored. A wide range of applications is possible, contingent on the energy densities of the specific photoisomers. Here, we report platinum-, copper-, and nickel-based heterogeneous catalysts screened in batch conditions for the back-conversion reaction on the cyano-3-(4-methoxyphenyl)-norbornadiene/quadricyclane pair. Catalyst reactivities are investigated using structural characterization, imaging techniques, and spectroscopic analysis. Finally, the thermal stability is also explored for our best-performing catalysts.

Flow-Integrated Preparation of Norbornadiene Precursors for Solar Thermal Energy Storage.

Molecular solar thermal (MOST) energy storage systems are getting increased attention related to renewable energy storage applications. Particularly, 2,3-difunctionalized norbornadiene-quadricyclane (NBD-QC) switches bearing a nitrile (CN) group as one of the two substituents are investigated as promising MOST candidates thanks to their high energy storage densities and their red-shifted absorbance. Moreover, such NBD systems can be prepared in large quantities (a requirement for MOST-device applications) in flow through Diels-Alder reaction between cyclopentadiene and appropriately functionalized propynenitriles. However, these acetylene precursors are traditionally prepared in batch from their corresponding acetophenones using reactive chemicals potentially leading to health and physical hazards, especially when working on a several-grams scale. Here, we develop a multistep flow-chemistry route to enhance the production of these crucial precursors. Furthermore, we assess the atom economy (AE) and the E-factor showing improved green metrics compared to classical batch methods. Our results pave the way for a complete flow synthesis of NBDs with a positive impact on green chemistry aspects.

Thermally enhanced nanocomposite phase change material slurry for solar-thermal energy storage

This paper investigates the photothermal conversion performance of an innovative heat transfer fluid containing nano-encapsulated phase change material (PCM) with metallic shell materials in a solar thermal energy storage system. The influences of shell thickness, core size, shell material type, PCM mass and shell volume concentrations on the thermal performance of the heat storage medium are investigated and compared. The results show that the heat transfer rates of water-based Ag, Au, Cu and Al nanofluids are 6.89, 5.86, 7.05 and 6.99 W, respectively, while slurries formed by adding paraffin@Ag, Au, Cu and Al nano capsules to pure water enhance heat transfer by 6.18, 13.38, 10.8 and 11.33 %, respectively. The metallic nanoparticle-based shell materials further augment the temperature and energy storage gains by enhancing the solar radiation capture capability of the heat storage medium. Specifically, depending on the mass concentration of PCM, the storage capacity of paraffin@Cu slurry is augmented by up to 290 %. As the shell thickness of the Ag particles also decreases from 8 to 2 nm, it augments the slurry's storage ability for thermal energy by 7 %. The enhancement in the dimensions of the nano capsules, however, causes the surface area-to-volume ratio (SA:V) to reduce the photothermal conversion of the slurry by clustering. Therefore, the thermal energy storage behaviour of the Paraffin@Cu slurry is diminished by 5 % as the core size enhances from 10 to 40 nm. Further, the augmentation in the volume concentration of Al particles in the shell surprisingly reduces the thermal energy storage by 5 %. Finally, paraffin-based solid PCM is also experimentally tested for validation of the specific heat capacity model at various wind speeds and solar radiation.

Performance investigation and evaluation of a low-temperature solar thermal energy storage system under dynamic weather conditions

Designed and operational parameters matter greatly in how successful an energy storage system performs. However, a current challenge in matching suitable these parameters lies in the poor understanding of such systems’ performance under dynamic weather conditions. In this paper, we investigated a phase change material (PCM) storage unit that is particularly aimed for poor-solar areas, and connected the unit to a flat plate solar collector to establish a complete solar thermal energy storage system (STESS). To optimize the system performance, different grades of solar radiation and outdoor ambient temperatures are introduced, and the effects of heat transfer fluid (HTF) flow rates and solar collecting areas are investigated numerically through multiple performance evaluation parameters. The results indicate that the solar collecting area has a significant effect on the performance of the STESS compared to that of the water flow rate. And different collecting areas of 1 m2, 1.5 m2, and 3 m2 with an optimal water flow rate of 0.06 m3/h are matched to different average daily solar radiation of 203.4 W/m2, 155.2 W/m2, 92.7 W/m2, respectively. Further for the heat release process, different heat release efficiencies from 88.32 % to 97.12 % with different energy consumption of the fan from 0.003 kWh to 0.063 kWh are obtained when the air flow rate is increased from 30 m3/h to 90 m3/h. One of the air flow rates of 60 m3/h is superior for the STESS considering higher heat release efficiency and lower energy consumption of the fan. The findings of this paper will contribute to optimizing the performance of a STESS in practical applications.

Development of NaCl-MgCl2-CaCl2 Ternary Salt for High-Temperature Thermal Energy Storage Using Machine Learning.

NaCl-MgCl2-CaCl2 eutectic ternary chloride salts are potential heat transfer and storage materials for high-temperature thermal energy storage. In this study, first-principles molecular dynamics simulation results were used as a data set to develop an interatomic potential for ternary chloride salts using a neural network machine learning method. Deep potential molecular dynamics (DPMD) simulations were performed to predict the microstructure and thermophysical properties of the NaCl-MgCl2-CaCl2 ternary salt. This work reveals that DPMD simulations can accurately calculate the microstructure and thermophysical properties of ternary chloride salts. The association strength of chloride ions and cations follows the order of Mg2+ > Ca2+ > Na+, and the coordination number decreases gradually with increasing temperature, indicating a progressively looser and more disordered molten structure. Furthermore, thermophysical properties, such as density, specific heat capacity, thermal conductivity, and viscosity, are in good agreement with the experimental measurements. Machine learning molecular dynamics will provide a feasible multivariate molten salt exploration method for the design of next-generation solar power plants and thermal energy storage systems.

A Review on the Nanofluids-PCMs Integrated Solutions for Solar Thermal Heat Transfer Enhancement Purposes

The current review offers a critical survey on published studies concerning the simultaneous use of PCMs and nanofluids for solar thermal energy storage and conversion processes. Also, the main thermophysical properties of PCMs and nanofluids are discussed in detail. On one hand, the properties of these types of nanofluids are analyzed, as well as those of the general types of nanofluids, like the thermal conductivity and latent heat capacity. On the other hand, there are specific characteristics of PCMs like, for instance, the phase-change duration and the phase-change temperature. Moreover, the main improvement techniques in order for PCMs and nanofluids to be used in solar thermal applications are described in detail, including the inclusion of highly thermal conductive nanoparticles and other nanostructures in nano-enhanced PCMs and PCMs with extended surfaces, among others. Regarding those improvement techniques, it was found that, for instance, nanofluids can enhance the thermal conductivity of the base fluids by up to 100%. In addition, it was also reported that the simultaneous use of PCMs and nanofluids enhances the overall, thermal, and electrical efficiencies of solar thermal energy storage systems and photovoltaic-nano-enhanced PCM systems. Finally, the main limitations and guidelines are summarized for future research in the technological and research fields of nanofluids and PCMs.

Modeling and analysis of PCM‐encapsulated solar thermal energy storage system for space heating

AbstractIn this study, a phase change material (PCM)‐encapsulated packed‐bed thermal energy storage (PB‐TES) system is intended for Day‐round space heating in the winter. Solar concentric collectors act for day‐time heating and TES charging, while the stored energy can be used at night and intermediate time for space heating. A region‐wise techno‐economic analysis of PCM candidates is made to compare the costs and sizes of solar collectors and PB‐TES. A spherical capsule filled with sodium nitrite (NaNO2) and sodium nitrate (NaNO3) is numerically investigated during the PCM charging at constant thermal input. After complete liquefication, the charging time for NaNO2 and NaNO3 capsules is 3280 and 4300 s, respectively, holding the maximum stored energy of 733.4 KJ/kg at 285°C and 687.27 kJ/kg at 310.12°C, respectively. In addition, the stored exergy is obtained 238.78 and 234.74 kJ/kg for NaNO2 and NaNO3, respectively; however, the average exergetic effectiveness for NaNO2 and NaNO3 are 0.54 and 0.46. Despite the lower energy storage capacity (kJ/kg) of NaNO3, the PB‐TES volume is less with NaNO3 than with NaNO2 due to higher density. However, the average cost ($/tonne) of NaNO3 PCM is 50% higher than NaNO2. Subsequently, the thermal efficiency of the proposed system is estimated at 27.68% and 26.94% during day and night‐time operations.

Experimental investigation of the solar latent heat thermal energy storage system integrated with salt hydrate phase-change materials

To achieve rational utilization of renewable energy sources, a solar latent heat thermal energy storage system for hot water application was developed in this study. The feasibility of the salt hydrates using in the solar heating was assessed and the comparative experimental investigation was conducted under various operating conditions. It shows that the higher flow rate and radiation accelerate the melting process of the phase-change material. The time taken for the storage medium to reach phase transition was reduced by approximately 48.9%; meanwhile, the collector efficiency was enhanced by approximately 10.2% as the flow rate increased from 10 g/s to 30 g/s. The accumulated charging energy increased by approximately 10.9% when the radiation increased from 850 W/m2 to 920 W/m2, resulting in a prolonged heat release process. The test results suggest the promising potential of the salt hydrates for the solar water heating applications.

Searching the Chemical Space of Bicyclic Dienes for Molecular Solar Thermal Energy Storage Candidates.

Photoswitches are molecular systems that are chemically transformed subsequent to interaction with light and they find potential application in many new technologies. The design and discovery of photoswitch candidates require intricate molecular engineering of a range of properties to optimize a candidate to a specific applications, a task which can be tackled efficiently using quantum chemical screening procedures. In this paper, we perform a large scale screening of approximately half a million bicyclic diene photoswitches in the context of molecular solar thermal energy storage using ab initio quantum chemical methods. We further device an efficient strategy for scoring the systems based on their predicted solar energy conversion efficiency and elucidate potential pitfalls of this approach. Our search through the chemical space of bicyclic dienes reveals systems with unprecedented solar energy conversion efficiencies and storage densities that show promising design guidelines for next generation molecular solar thermal energy storage systems.

Searching the Chemical Space of Bicyclic Dienes for Molecular Solar Thermal Energy Storage Candidates

AbstractPhotoswitches are molecular systems that are chemically transformed subsequent to interaction with light and they find potential application in many new technologies. The design and discovery of photoswitch candidates require intricate molecular engineering of a range of properties to optimize a candidate to a specific applications, a task which can be tackled efficiently using quantum chemical screening procedures. In this paper, we perform a large scale screening of approximately half a million bicyclic diene photoswitches in the context of molecular solar thermal energy storage using ab initio quantum chemical methods. We further device an efficient strategy for scoring the systems based on their predicted solar energy conversion efficiency and elucidate potential pitfalls of this approach. Our search through the chemical space of bicyclic dienes reveals systems with unprecedented solar energy conversion efficiencies and storage densities that show promising design guidelines for next generation molecular solar thermal energy storage systems.

Surface science and liquid phase investigations of oxanorbornadiene/oxaquadricyclane ester derivatives as molecular solar thermal energy storage systems on Pt(111).

The transition to renewable energy sources comes along with the search for new energy storage solutions. Molecular solar thermal systems directly harvest and store solar energy in a chemical manner. By a suitable molecular design, a higher overall efficiency can be achieved. In this study, we investigate the surface chemistry of oxa-norbornadiene/quadricyclane derivatives on a Pt(111) surface. Specifically, we focus on the energy storage and release properties of molecules that are substituted with ester moieties of different sizes. For our model catalytic approach, synchrotron radiation-based x-ray photoelectron spectroscopy measurements were conducted in ultra-high vacuum (UHV) and correlated with the catalytic behavior in the liquid phase monitored by photochemical infrared reflection absorption spectroscopy. The differences in their spectral appearance enabled us to unambiguously differentiate the energy-lean and energy-rich isomers and decomposition products. Next to qualitative information on the adsorption motifs, temperature-programmed experiments allowed for the observation of thermally induced reactions and the deduction of the related reaction pathways. We analyzed the selectivity of the cycloreversion reaction from the energy-rich quadricyclane derivative to its energy-lean norbornadiene isomer and competing processes, such as desorption and decomposition. For the 2,3-bis(methylester)-substitution, the cycloreversion reaction was found to occur between 310 and 340K, while the thermal stability limit of the compounds was determined to be 380K. The larger 2,3-bis(benzylester) derivatives have a lower apparent adsorption energy and a decomposition onset already at 135K. In the liquid phase (in acetonitrile), we determined the rate constants for the cycloreversion reaction on Pt(111) to k = 5.3 × 10-4s-1 for the 2,3-bis(methylester)-substitution and k = 6.3 × 10-4s-1 for the 2,3-bis(benzylester) derivative. The selectivities were of >99% and 98% for the two molecules, respectively. The difference in the catalytic behavior of Pt(111) for both derivatives is less pronounced in the liquid phase than in UHV, which we attribute to the passivation of the Pt(111) surface by carbonaceous species under ambient conditions.

Bis‐ and Tris‐norbornadienes with High Energy Densities for Efficient Molecular Solar Thermal Energy Storage

AbstractMolecular solar thermal energy storage (MOST) systems can convert, store and release solar energy in chemical bonds, i.e., as chemical energy. In this work, phenyl‐ and naphthyl‐linked bis‐ and tris‐norbornadienes are presented as promising MOST systems with very high energy densities. The substrates were synthesized by Suzuki–Miyaura coupling reactions and their absorption properties and characteristic parameters for MOST applications were investigated. The norbornadiene derivatives showed absorption onsets of up to 386 nm and photoisomerization quantum yields of 56 % per photoisomerization event. The resulting quadricyclane products have half‐lifes up to 14 d and very high energy densities of up to 734 kJ/kg. Overall, these norbornadienes fulfill necessary criteria for an optimal MOST system and are, therefore, a highly promising basis for the development of materials for efficient solar energy conversion and storage.

Bis- and Tris-norbornadienes with High Energy Densities for Efficient Molecular Solar Thermal Energy Storage.

Molecular solar thermal energy storage (MOST) systems can convert, store and release solar energy in chemical bonds, i.e., as chemical energy. In this work, phenyl- and naphthyl-linked bis- and tris-norbornadienes are presented as promising MOST systems with very high energy densities. The substrates were synthesized by Suzuki-Miyaura coupling reactions and their absorption properties and characteristic parameters for MOST applications were investigated. The norbornadiene derivatives showed absorption onsets of up to 386 nm and photoisomerization quantum yields of 56% per photoisomerization event. The resulting quadricyclane products have half-lifes up to 14 d and very high energy densities of up to 734 KJ/Kg. Overall, these norbornadienes fulfill necessary criteria for an optimal MOST system and are, therefore, a highly promising basis for the development of materials for efficient solar energy conversion and storage.

Dynamic characteristics and energy efficiency evaluation of a novel solar seasonal thermal storage - heating system

This paper proposes solar seasonal thermal energy storage system compounded with long-term and short-term energy storage tanks for a single-family dwelling, which using assisted water source heat pump to further improve the systems stability. With the objective of improving the solar energy utilization efficiency and reducing the primary energy consumption, the dynamic simulation model of the “heat collection-heat storage-heat supply” system under the non-stationary boundary conditions throughout the year is established. The energy transfer and conversion law of each subsystem and the dynamic operation characteristics are analyzed through simulation method. The system cooperative control strategy is proposed and parameter optimization is carried out. Results indicate that the annual heat collection efficiency of the water source heat pump composite system has been improved by 2.2 % compared with the electric auxiliary heating system. Meanwhile, the heat storage efficiency and the solar energy guarantee rate increased by 5.8 % and 8.3 %, respectively. Moreover, the optimal water source heat pump composite system not only improves energy efficiency and achieves the cost savings compared with the electric auxiliary heating system, but also reduces carbon dioxide emission by 10.3 %, which have great advantages for energy saving and emission reduction.