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Research Project
Coimbra Chemistry Center
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Publications
Low temperature energy storage PCM systems: phase equilibrium studies
Publication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Fausto, Rui
Solid-liquid phase equilibrium: alkane systems for low temperature energy storage
Publication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Fausto, Rui
The incessant and increasing need for energy requires urgent and effective solutions. The supply of renewable energies is mainly intermittent, which often leads to a gap between the availability of energy and its consumption. Therefore, energy storage becomes imperative for increasing the efficiency in the use of the produced energy. Concerning this, the use of phase change materials (PCMs) has taken a very important role, especially for active cooling systems. In particular, eutectic systems can be designed with characteristics that make them suitable for each application, allowing significant energy savings, which is very relevant in what concerns economic and environmental sustainability [1].
This work aims to the characterization of selected systems that can be used for energy storage at low temperatures, starting by the construction of solid-liquid phase diagrams using differential scanning calorimetry (DSC) and Raman Spectroscopy results. Phase diagrams are crucial to characterize the behaviour of these systems and reveals the robustness of the PCM, and for new PCMs, equilibrium studies are essential to achieve the desired melting temperature [2].
This work is focused on binary systems composed by normal alkanes, in particular, the binary mixtures C8-C10 and C10-C12. These systems revealed to behave as eutectic systems at low temperatures, showing a promising applicability for thermal energy storage for low temperature applications. The eutectic points are around -61ºC and -35ºC, respectively. Additionally, a fitting equation for the experimental liquidus lines of the phase equilibrium diagrams is proposed for each system.
Adipates as new phase change material: seeking for a low temperature energy storage system
Publication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Fausto, Rui
The recent and endless increasing need for energy is requiring imperative and efficient solutions. Renewable energies are an effective solution, but they are also intermittent, which often leads to a gap between the availability of energy and its demand. Therefore, energy storage becomes crucial for improving the efficiency by reducing the mismatch between demand and supply thus offering better management capabilities. The use of phase change materials (PCMs) became an attractive technology, especially for active cooling systems. In particular, eutectic systems can be designed for each application, allowing significant energy savings, which is very relevant in what concerns economic and environmental sustainability [1].
Equilibrium studies and their phase diagrams are crucial to characterize the behavior of these systems, particularly for new PCMs [2].
This work aims the characterization of a selected type of binary system composed by di-n-alkyl adipates that can be used for energy storage at low temperatures, starting by the construction of solid-liquid phase diagram based on Differential Scanning Calorimetry (DSC) and Raman Spectroscopy results.
The studied system is a binary mixture of diethyl and dibutyl adipates and reveals to behave as a eutectic system at low temperatures, possessing also polymorphism, therefore presenting a relatively complex phase diagram. The eutectic point was found around -33ºC and the polymorphism transition, being characteristic of the dibutyl adipate, occurs at around -36ºC for the overall phase diagram. Raman spectroscopy was fundamental concerning the construction of the phase diagram, enabling to identify the different solid and liquid phases of the system.
This work provides new phase equilibrium data, which, to the knowledge of the authors, are the first in the literature, concerning these compounds. The studied binary system has promising characteristics for low temperature energy storage. It is also demonstrated how solid-liquid-phase equilibrium studies are the key to select the most appropriate phase change material for a specific thermal energy storage (TES) application.
Di-Alkyl adipates as new phase change material for low temperature energy storage
Publication . Sequeira, Maria Carolina; Nogueira, Bernardo A.; Caetano, Fernando J. P.; Diogo, Herminio; Fareleira, João M. N. A.; Fausto, Rui
This work is a contribution to the thermal characterization of a selected binary system of two di-n-alkyl adipates that can be used as phase change material for thermal energy storage at low temperatures. The construction of the solid–liquid phase diagram using differential scanning calorimetry (DSC), complemented with Raman Spectroscopy studies for the system composed by diethyl and dibutyl adipates is presented. The solidus and liquidus equilibrium temperatures were determined by DSC for the pure components and 30 binary mixtures at selected molar compositions were used to construct the corresponding solid–liquid phase diagram. The binary system of diethyl and dibutyl adipates presents eutectic behaviour at low temperatures. The eutectic temperature was found at 240.46 K, and the eutectic composition was determined to occur at the molar fraction xdibutyl = 0.46. Additionally, the system shows a polymorphic transition, characteristic of dibutyl adipate, occurring at ca. 238 K, confirmed by optical microscopy. To the best of our knowledge, no reference to the phase diagram of the present system could be found in the literature. Raman spectroscopy was essential to complement the construction of the phase equilibrium diagram, enabling the identification of the solid and liquid phases of the system. Finally, the liquidus curve of the phase diagram was also successfully predicted using a suitable fitting equation, being the root mean square deviation of the data from the correlation equal to 0.54 K. In addition, this fitting operation enabled a correct prediction of the eutectic composition of the system.
Thermophysical properties of n-alkane system for low temperature thermal energy storage
Publication . Nogueira, Bernardo A.; Nikitin, Timur; Diogo, Hermínio P.; Fausto, Rui; Fareleira, João; Caetano, Fernando J. P.; Sequeira, Maria Carolina
Over the past few decades, the escalating need for energy has posed a significant and pressing challenge. For centuries, fossil fuels stood as the dominant energy source; however, due to their dwindling availability and environmental complications, renewable energies have emerged as the promising solution for the future [1]. The intermittent nature of renewable energy sources often results in a disconnect between energy production and consumption, underscoring the vital role of energy storage technologies in enhancing clean energy utilization [2]. Among various energy storage solutions, thermal energy storage (TES) shines as one of the most promising options, offering substantial energy storage capacity at a relatively low cost [3]. In this context, phase change materials (PCMs) are particularly crucial, namelyfor active cooling systems. N-alkanes have been widely investigated for TES applications due to their singular characteristics including their phase transition performance, among others [4].
The objective of this work is to characterize selected n-alkane systems, involving the construction of the solid-liquid binary phase diagrams, using differential scanning calorimetry (DSC) and Raman Spectroscopy. Additionally, the present research efforts seek to obtain the thermal conductivity of these systems. The ongoing investigations play a critical role towards understanding the properties of these systems, enabling to predict their thermal characteristics and performance as PCMs for TES applications. Particularly, for new PCMs phase equilibrium studies are essential to select the appropriate systems with the desired properties for each application.
This work is focused on binary systems composed by odd and even alkanes, in particular the binary mixtures C8–C10, C9–C10, C9–C11 and C10–C12. These systems revealed different solid-liquid phase equilibrium behaviour at low temperatures, although three of these four systems exhibited promising capabilities to be used for TES applications at low temperatures. Detailed results on these binary systems will be presented and discussed.
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Funding agency
Fundação para a Ciência e a Tecnologia
Funding programme
6817 - DCRRNI ID
Funding Award Number
UIDP/00313/2020