Solid-state Li-ion batteries operating at room temperature using new borohydride argyrodite electrolytes

Using a new class of (BH4)- substituted argyrodite Li6PS5Z0.83(BH4)0.17, (Z = Cl, I) solid electrolyte, Li-metal solid-state batteries operating at room temperature have been developed. The cells were made by combining the modified argyrodite with an In-Li anode and two types of cathode: an oxide, LixMO2 (M = 1/3Ni, 1/3Mn, 1/3Co; so called NMC) and a titanium disulfide, TiS2. The performance of the cells was evaluated through galvanostatic cycling and Alternating Current AC electrochemical impedance measurements. Reversible capacities were observed for both cathodes for at least tens of cycles. However, the high-voltage oxide cathode cell shows lower reversible capacity and larger fading upon cycling than the sulfide one. The AC impedance measurements revealed an increasing interfacial resistance at the cathode side for the oxide cathode inducing the capacity fading. This resistance was attributed to the intrinsic poor conductivity of NMC and interfacial reactions between the oxide material and the argyrodite electrolyte. On the contrary, the low interfacial resistance of the TiS2 cell during cycling evidences a better chemical compatibility between this active material and substituted argyrodites, allowing full cycling of the cathode material, 240 mAhg-1, for at least 35 cycles with a coulombic efficiency above 97%

A Case Study of Thermal Evolution in the Vicinity of Geothermal Probes Following a Distributed TRT Method

[EN] To meet the stated climate change targets and to ensure the capability of meeting the current and future energy demands, there is an urgent need to develop renewable energy sources, such as geothermal systems. If geothermal systems are to be cost-efficient and are to enjoy public confidence, it is essential that they are designed and installed in accordance with the prevailing site-specific conditions. A thorough understanding of the thermal behaviour of the surrounding ground is, therefore, critical. In this work, we investigated temperature and its evolution in the vicinity of a shallow geothermal helix-shaped borehole heat exchanger (BHE). To measure the temperature close to the actual geothermal system, an additional U-tube probe was installed at the edge of the same borehole. A thermal load was then applied to the BHE, and the temperature was detected in the nearby U-tube. The temperature measurements were made with a GEOSniff monitoring device. To understand these localised temperature measurements in the context of the Valencia test site, ERT measurements were also performed. The GEOSniff device permits measurements to be made with very high depth resolution, which allows the thermal properties of the surrounding ground to be derived precisely, thus, enabling the identification of the different textural domains.This research work has been supported financially by the European Cheap-GSHPs Project (funded by the European Union's Horizon 2020 research and innovation program under grant agreement No 657982) and by the European GEO4CIVHIC Project (funded by the European Union's Horizon 2020 research and innovation program under grant agreement No 792355).Schwarz, H.; Badenes Badenes, B.; Wagner, J.; Cuevas, JM.; Urchueguía Schölzel, JF.; Bertermann, D. (2021). A Case Study of Thermal Evolution in the Vicinity of Geothermal Probes Following a Distributed TRT Method. Energies. 14(9):1-17. https://doi.org/10.3390/en14092632S11714

Spatial analysis of indicators affecting the exploitation of shallow geothermal energy at European scale

Shallow Geothermal Energy (SGE) exploited by vertical close loop Ground Source Heat Pumps (GSHP) is a proven, reliable, and widespread renewable heating and cooling technology. However, in many regions there is still a lack of awareness among policy makers and end users, constituting a major constraint to wider deployment of SGE. In order to contribute to its market consolidation, this work focuses on bringing to light relevant spatial information affecting the suitability of SGE exploitation. This information is the result of the systematization of geological, climatic, and environmental open and available data translated into performance indicators. A set of thematic maps was created using Geographic Information Systems (GIS) comprising the European Member States and other European countries. The relative area and the amount of population affected per indicator was spatially analyzed to determine the most common values found and the affected population. The relationship between area percentage and population affected percentage per indicator was also analyzed and allowed to identify the most common indicators values in areas where high energy demands are expected. Additionally, an example of how this data can be used into a Multi-Criteria Decision-Making (MCDM) framework is shown.This article is part of a project that has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 727583 (GEOCOND). This work was partially supported by the Spanish Ministry of Economy and Competitiveness (MINECO), reference TIN2017e86647eP. The authors also acknowledge the support of the Fundación Séeneca (Region of Murcia, Spain) through the Grant 19882eGERMe15

Sensor Array-Based Optical Portable Instrument For Determination Of Ph

A portable optical instrument is presented that makes it possible to determine pH with a colorimetric sensor array. The use of four membranes containing acid-base indicators makes it possible to cover the full range of pH using the H (hue) coordinate measurements of the HSV colour space. pH sensitive membranes were directly cast onto a plastic support to form a two-dimensional array, located between an OLED display as the programmable light source and a set of digital colour detectors. The resulting microcontroller-based system is immune to optical and electrical interferences. A complete optical and electrical characterization and optimization of the hand-held instrument was carried out. The instrument was used to determine pH using a simple algorithm to select the sensor output that was programmed in the microcontroller. The initial eleven candidate pH membranes were reduced to only four, which permit to obtain reliable pH values. The pH response of the selected four sensing elements was modelled, and calibration curves were applied to a validation set and real samples obtaining positive correlations between the real and predicted data.Ministerio de Ciencia e Innovación, Dirección General de Investigación y Gestión del Plan Nacional de I+D+i (Spain) (Projects CTQ2009-14428-C02-01 and CTQ2009-14428-C02-02)Junta de Andalucía (Proyecto de Excelencia P08-FQM-3535)Partially supported by European Regional Development Funds (ERDF

Changes in Anxiety and Depression Traits Induced by Energy Restriction: Predictive Value of the Baseline Status

Current evidence proposes diet quality as a modifiable risk factor for mental or emotional impairments. However, additional studies are required to investigate the effect of dietary patterns and weight loss on improving psychological symptoms. The aim of this investigation was to evaluate the effect of energy-restriction, prescribed to overweight and obese participants, on anxiety and depression symptoms, as well as the potential predictive value of some baseline psychological features on weight loss. Overweight and obese participants (n = 305) were randomly assigned for 16 weeks to two hypocaloric diets with different macronutrient distribution: a moderately high-protein (MHP) diet and a low-fat (LF) diet. Anthropometrical, clinical, psychological, and lifestyle characteristics were assessed at baseline and at the end of the intervention. The nutritional intervention evidenced that weight loss has a beneficial effect on trait anxiety score in women (β = 0.24, p = 0.03), depression score in all population (β = 0.15, p = 0.02), particularly in women (β = 0.22, p = 0.03) and in subjects who followed the LF diet (β = 0.22, p = 0.04). Moreover, weight loss could be predicted by anxiety status at baseline, mainly in women and in those who were prescribed a LF diet. This trial suggests that weight loss triggers an improvement in psychological traits, and that anxiety symptoms could predict those volunteers that benefit most from a balanced calorie-restricted intervention, which will contribute to individualized precision nutrition

Development of advanced materials guided by numerical simulations to improve performance and cost-efficiency of borehole heat exchangers (BHEs)

[EN] One promising way to improve the efficiency of borehole heat exchangers (BHEs) in shallow geothermal applications is to enhance the thermal properties of the materials involved in its construction. Early attempts, such as using metal tubes in the 1980s or the utilization of thin-foil hoses, did not succeed in being adopted by the market for diverse reasons (cost, corrosion, fragility, etc...). In parallel, the optimization of pipe size, the use of double-U-tubes, thermally enhanced grout, etc. were able to bring the measure for the BHE efficiency, the borehole thermal resistance, from 0.20 to 0.15 K/(Wm) down to 0.08-0.06 K/(Wm) in the best solutions today. A further improvement cannot be expected without development of new, dedicated materials, combining the versatility of plastic like PE with an increased thermal conductivity that matches the respective properties of the rock and soil. This goal was included in the Strategic Research and Innovation Agenda of the European Technology Platform on Renewable Heating and Cooling in 2013. Within an EU supported project, both BHE pipes and grouting materials have been produced prototypically in small amounts, suitable for the first tests in the intended environment. The present work explains the research pathways envisaged and the resulting sensitivity analysis to highlight the influence of some of the most critical parameters that affect the overall performance of a GSHP system. The results have allowed guiding the real development of more efficient new advanced materials for different scenarios representative of different European regions. Finally the developed materials and their properties are discussed, including a comparative assessment about their compliance with reference material properties as currently seen in the BHE market.This article is part of a project that has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement No 727583.Badenes Badenes, B.; Sanner, B.; Mateo Pla, MÁ.; Cuevas, JM.; Bartoli, F.; Ciardelli, F.; González, RM.... (2020). Development of advanced materials guided by numerical simulations to improve performance and cost-efficiency of borehole heat exchangers (BHEs). Energy. 201:1-17. https://doi.org/10.1016/j.energy.2020.117628117201Alva, G., Lin, Y., & Fang, G. (2018). An overview of thermal energy storage systems. Energy, 144, 341-378. doi:10.1016/j.energy.2017.12.037Li, H., Xu, W., Yu, Z., Wu, J., & Sun, Z. (2017). Application analyze of a ground source heat pump system in a nearly zero energy building in China. Energy, 125, 140-151. doi:10.1016/j.energy.2017.02.108Ozgener, O. (2010). Use of solar assisted geothermal heat pump and small wind turbine systems for heating agricultural and residential buildings. Energy, 35(1), 262-268. doi:10.1016/j.energy.2009.09.018Jensen, J. K., Ommen, T., Markussen, W. B., & Elmegaard, B. (2017). Design of serially connected district heating heat pumps utilising a geothermal heat source. Energy, 137, 865-877. doi:10.1016/j.energy.2017.03.164A. C. Crandall, House heating with earth heat pump, Electr World, 126/19, 94-5 (1946).Moegle, E. (2009). Earth- and buildingsided characteristics of a geothermal energy field with five coaxial tubes erected in 1974 in Schoenaich (County of Boeblingen) – a contribution to history for near-surface geothermic drilling in Europe. Jahresberichte und Mitteilungen des Oberrheinischen Geologischen Vereins, 91, 31-35. doi:10.1127/jmogv/91/2009/31Lundh, M., & Dalenbäck, J.-O. (2008). Swedish solar heated residential area with seasonal storage in rock: Initial evaluation. Renewable Energy, 33(4), 703-711. doi:10.1016/j.renene.2007.03.024Ground coupled heat pumps of high technology - groundhit, Funded by FP6-SUSTDEV - sustainable development, global change and ecosystems: thematic priority 6 under the focusing and integrating community research programme 2002-2006. Project ID: 503063.Go, G.-H., Lee, S.-R., Yoon, S., Park, H., & Park, Sk. (2014). Estimation and experimental validation of borehole thermal resistance. KSCE Journal of Civil Engineering, 18(4), 992-1000. doi:10.1007/s12205-014-0454-xZhang, S., Huang, Z., Li, G., Wu, X., Peng, C., & Zhang, W. (2018). Numerical analysis of transient conjugate heat transfer and thermal stress distribution in geothermal drilling with high-pressure liquid nitrogen jet. Applied Thermal Engineering, 129, 1348-1357. doi:10.1016/j.applthermaleng.2017.10.042Fossa, M., & Minchio, F. (2013). The effect of borefield geometry and ground thermal load profile on hourly thermal response of geothermal heat pump systems. Energy, 51, 323-329. doi:10.1016/j.energy.2012.12.043SPIN-PET, Via R. Piaggio, 32, 56025, Pontedera ,Italy, http://www.spinpet.it//, [Online; accessed 12-December-2019].SILMA, Via Lombardia 97/00/101, Poggio a Caiano, Italy, http://www.spinpet.it//, [Online; accessed 12-December-2019].AIMPLAS, Plastics Technology Centre, Paterna, Spain, https://www.aimplas.net/aimplas/, [Online; accessed 12-December-2019].CAUDAL - Extruline Systems, Puerto Lumbreras (Murcia), Spain, https://www.caudal.es/index.php/en/, [Online; accessed 12-December-2019].ASTM C 666: [Standard Test Method for Resistance of Concrete to Rapid Freezing and Thawing].ASTM C 531-85: Standard test method for linear shrinkage and coefficient of thermal expansion of chemical-resistant mortars, grouts, monolithic surfacings, and polymer concretes.EN 197-1: Cement - Part 1: composition, specifications and conformity criteria for common cements.EN 445: Grout for prestressing tendons - test methods.SS 137244: Concrete testing – hardened concrete – scaling at freezing.RISE Research Institutes of Sweden, Division Samhällsbyggnad – Infrastructure and Concrete Construction, Stockholm, Sweden, https://www.ri.se/sv, [Online; accessed 12-December-2019].UBeG GbR, Wetzlar, Germany, http://www.ubeg.de. [Online; accessed 12-December-2019]

How Reliable Are Standard Thermal Response Tests? An Assessment Based on Long-TermThermal Response Tests Under Different Operational Conditions

[EN] In this contribution, we analyze the results of a number of thermal response test (TRT) experiments performed during several years at the same location at our university campus in Valencia (Spain), a permeable saturated soil area with possible groundwater flow conditions. A combination of different heat injection rates, TRT operation times of up to 32 days, and various methods for parameter estimation of ground thermal properties have been applied to study their influence on the result and accuracy of TRTs. Our main objective has been to experimentally quantify the influence of groundwater flow heat advection using moving infinite and finite line-source theories, as well as to analyze the influence of factors such as test duration, sensor accuracy, and external thermal influences. We have shown that the traditionally used infinite and finite line-source models, as well as the moving line-source models, can accurately represent experimental temperature evolution, but that there are many caveats regarding the significance parameters extracted and its reproducibility and stability. These features can be improved if data from the first test days are disregarded for the analysis, obtaining a much faster convergence to the definitive soil parameter estimates, including the effective Peclet number that represents groundwater flow in our particular case.This research was funded by the European Union's Horizon 2020 Research and Innovation program under grant agreement No [657982] and [727583].Urchueguía Schölzel, JF.; Lemus Zúñiga, LG.; Oliver Villanueva, JV.; Badenes Badenes, B.; Mateo Pla, MÁ.; Cuevas-Castell, JM. (2018). How Reliable Are Standard Thermal Response Tests? An Assessment Based on Long-TermThermal Response Tests Under Different Operational Conditions. Energies. 11(12). https://doi.org/10.3390/en11123347S111

Avaliação da eficácia da esterilização do instrumental odontológico na clínica de odontologia de Unibe

Introduction: In the field of dentistry, one way to prevent cross-contamination between patients is by eliminating blood waste and other fluids that have been obtained during the use of instruments. The objective of this research was to evaluate the effectiveness of autoclaving dental instruments in the areas of Endodontics and Periodontics. Methods: An in-vitro, experimental and cross-sectional study was performed on a population of 75 students in comprehensive clinics iii, iv and v at the Unibe dental clinic. 60 samples were taken using smears, which were then inoculation on chromo-agar orientation petri plates and subsequently incubated. The sample consisted of: 10 endodontic files in closed boxes before sterilization in the autoclave, the same 10 endodontic files after sterilization in the autoclave, 10 periodontal instruments (curettes and scalers) before and after sterilization in the autoclave with cloths in perforated boxes, and 10 periodontal instruments before and after sterilization in the autoclave with pouches in perforated boxes.  Conclusion: 60% of the endodontic files after sterilization were found not to be contaminated and 69% for both cloths and pouches had no contamination.Introducción: en el área de la odontología, una de las maneras para prevenir que se produzca una contaminación cruzada entre pacientes es eliminando los residuos de sangre y otros fluidos que han sido obtenidos durante la utilización de los instrumentos. El objetivo de esta investigación es evaluar la eficacia de la esterilización en la autoclave del instrumental odontológico del Área de Endodoncia y Periodoncia. Métodos: se realizó un estudio in vitro, experimental y transversal en una población de 75 estudiantes que se encuentran en la clínica integral III, IV y V de la clínica dental de Unibe. Se tomaron 60 muestras, a las cuales se les realizó un frotis; estas fueron inoculadas en placas petris cromo-agar orientación y posteriormente incubadas. La muestra estuvo constituida por 10 limas endodónticas en cajas cerradas antes de esterilizar en la autoclave, 10 limas endodónticas después de esterilizar en la autoclave, 10 instrumentos periodontales (curetas y jaquetes) antes de esterilizar en paños en la autoclave en cajas perforadas, 10 de los mismos instrumentos después de esterilizar en paños en la autoclave, 10 instrumentos periodontales antes de esterilizar en fundas en la autoclave en cajas perforadas y estas mismas 10 después de haber sido esterilizadas en fundas en la autoclave. Conclusión: se determinó que el 60% de las limas, después de esterilizar, no estaba contaminado y que el 69%, para ambos paños y fundas, no presentaba contaminación.  Introdução: na área da odontologia, uma das maneiras para prevenir que se produza uma contaminação cruzada entre pacientes é quando se eliminam os resíduos de sangue e outros fluídos que foram obtidos durante a utilização dos instrumentos. O objetivo desta pesquisa é avaliar a eficácia da esterilização na autoclave do instrumental odon-tológico da Área de Endodontia e Periodontia. Métodos: realizou-se um estudo in vitro, experimental e transversal na população de 75 estudantes que se encontram na clínica integral iii, iv e v da clínica dental de Uni-be. Tomaram-se 60 amostras, nas quais foi realizado um esfregaço; estas foram inoculadas em placas de Petri cromo-agar orientação e, posterior-mente, incubadas. A amostra esteve constituída por 10 limas endodôn-ticas em caixas fechadas antes de esterilizar na autoclave, 10 limas endo-dônticas depois de esterilizar na autoclave, 10 instrumentos periodontais (curetas e jaquetas) antes de esterilizar em panos na autoclave em caixas perfuradas, 10 dos mesmos instrumentos depois de esterilizar em panos autoclave, 10 instrumentos periodontais antes de esterilizar em bolsas de autoclave em caixas perfuradas e estas mesmas 10 depois de terem sido esterilizadas em bolsas na autoclave. Conclusão: determinou-se que 60% das limas, depois de esterilizar, não estavam contaminadas e que 69%, para ambos os panos e bolsas, não apresentavam contaminação

Nouveaux matériaux riches en Mg pour le stockage d'hydrogène (composés Mg6Pd1-xMTx (MT = Ni, Ag, Cu) massifs et nanoconfinés et nanocomposites MgH2-TiH2)

Cette thèse est consacrée à l'étude de composés riches en magnésium innovants destinés au stockage solide de l'hydrogène. Le but est de déstabiliser l'hydrure de Mg et d'accélérer sa cinétique de sorption par des effets d'alliage et de nano-structuration. La première famille de composés concerne les phases pseudo-binaires Mg6Pd1-xMTx (MT = Ni, Ag, Cu). Leurs propriétés structurales et les effets de substitution du Pd ont été étudiés par diffraction des rayons X, microscopie électronique à balayage et microsonde de Castaing. Les propriétés thermodynamiques et cinétiques d'hydrogénation de ces matériaux ont ensuite été déterminées par réaction solide-gaz. Différents mécanismes d'hydrogénation sont mis en jeu en fonction de l'élément de substitution. La nature des phases formées lors de la réaction d'hydrogénation modifie la stabilité des systèmes métal-hydrogène. Ainsi, la transformation de métal à hydrure est caractérisée par au moins deux plateaux de pression. Le premier plateau a lieu à une pression proche de celle de Mg/MgH2, alors que le second se produit à pression plus élevée. La détermination des valeurs d'enthalpie et d'entropie de réaction ont permis de quantifier la déstabilisation atteinte. Les meilleures cinétiques de désorption sont obtenues pour l'alliage au Ni, grâce à l'effet catalytique de la phase Mg2NiH4 formée lors de l'hydrogénation. La seconde approche vise à combiner les effets d'alliage et de nano-structuration. Des nanoparticules de Mg6Pd atteignant des tailles aussi petites que 3 nm sont confinées dans des matrices carbonées nano-poreuses. En comparant leurs propriétés d'hydrogénation à celles de l'alliage massif équivalent, on démontre non seulement que la cinétique de (dés)hydrogénation des nanoparticules est bien plus rapide, mais aussi que leur état hydrogéné est déstabilisé. Enfin, des nano-composites MgH2-TiH2 ont été synthétisés par broyage mécanique sous atmosphère réactive. L'ajout d'un catalyseur (TiH2) et la nano-structuration du Mg permettent de considérablement accélérer les cinétiques d'absorption et désorption d'hydrogène dans le Mg. Afin de comprendre le rôle de la phase TiH2 sur les propriétés cinétiques remarquables de ces nano-composites, leurs propriétés structurales ont été déterminées par diffraction des rayons X et des neutrons. L'existence d'une interface cohérente entre les phases Mg et TiH2 est d'importance majeure pour faciliter la mobilité de H au sein du nano-composite. De plus, il est démontré que les inclusions de TiH2 freinent la croissance de grain de Mg/MgH2, permettant ainsi de maintenir la nano-structuration des composés lors de leur cyclageThis thesis is dedicated to the study of novel magnesium-rich compounds for solid state hydrogen storage. The aim is to destabilize Mg hydride and accelerate its sorption kinetics by alloying and nanostructuration. The first family of compounds concerns the Mg6Pd1-xTMx (TM = Ni, Ag, Cu) pseudo-binary phases. Their structural properties and the effects of Pd substitution have been studied by X-ray diffraction, scanning electron microscopy and electron microprobe analyses. Their thermodynamics and kinetics of hydrogenation have been determined by solid-gas reaction. Different hydrogenation mechanisms take place depending on the substituting element. The stability of the metal-hydrogen system is altered by the nature of the phases formed during hydrogenation reaction. Thus, metal to hydride transformation is characterized by at least two absorption plateau pressures. The pressure of the first plateau is similar to that of Mg/MgH2 while the second one occurs at higher pressure. The enthalpy and entropy of reaction are determined to quantify the destabilizing effect of Pd by TM substitution. Best desorption kinetics are found for the Ni containing alloy thanks to the catalytic effect of the Mg2NiH4 phase formed on hydrogenation. The second approach aims to combine alloying with nanostructuration effects. Nanoparticles of Mg6Pd as small as 3 nm are confined into nanoporous carbon matrix. By comparing their hydrogenation properties with those of the bulk alloy, we demonstrate that not only the (de)hydrogenation kinetics are much faster for the nanoparticles, but also that their hydrided state is destabilized. Finally, MgH2-TiH2 nanocomposites were synthesized by mechanical milling under reactive atmosphere. The addition of a catalyst (TiH2) and Mg nanostructuration allow strongly accelerating the sorption kinetics of hydrogen in Mg. To understand the role of the TiH2 phase on the outstanding kinetics of these nanocomposites, their structural properties have been determined by X-ray and neutron diffraction. The existence of a coherent interface between Mg and TiH2 phases is of major importance to facilitate H-mobility within the nanocomposite. Furthermore, it is shown that the TiH2 inclusions inhibit the Mg/MgH2 grain growth, thus maintaining the composites nanostructure during their cyclingPARIS-EST-Université (770839901) / SudocSudocFranceF