Literatura científica selecionada sobre o tema "Couche de diffusion (GDL)"

The gas diffusion layer (GDL) is a crucial component of Proton Exchange Membrane Fuel Cells (PEMFC), water flooding will occur during the operation of PEMFC, resulting in performance degradation, and its water management plays a significant role in PEMFC performance. To investigate the transport mechanism of liquid water in GDL, the lattice Boltzmann method to simulate the behavior of GDL droplets using the 'random reconstruction' method. The accuracy of this model by calculating the tortuosity and comparing it with reported results in literature. The effects of different GDL structural parameters on permeability were studied. Finally, the conductivity and thermal conductivity of the GDL in various directions were examined. The results indicate that the porosity error of the three-dimensional structure model of GDL is within 0.01, enabling a realistic simulation of the GDL structure. The average error between the calculated results and the Bruggeman equation is only 2.5362%, and the average error compared to the reference results is less than 6%, demonstrating the model's high accuracy. As the porosity and fiber diameter of the GDL three-dimensional structure model increase, the permeability also increases. Conversely, the permeability decreases with an increase in the thickness of the GDL three-dimensional structure model. Moreover, an increase in GDL porosity leads to a gradual decrease in electrical conductivity and thermal conductivity in both the thickness and plane directions, with a more pronounced effect on the thickness. This study uncovers the transport characteristics of liquid water in the gas diffusion layer, which can inform the optimization of GDL structure design and serve as a theoretical reference for enhancing water management in proton exchange membrane fuel cells. Future research directions will focus on further optimizing the three-dimensional structure of GDL to improve its transmission characteristics and overall performance.

Abstract. Polymer electrolyte membrane fuel cells (PEMFCs) are considered as zero emission power sources for transportation and stationary power purposes. The membrane electrode assembly (MEA) is the core of PEMFC and is composed of a gas diffusion layer (GDL), catalyst layer (CL) and proton exchange membrane (PEM). GDL is a carbon-based, fibrous porous medium that simultaneously provides a path for heat, mass and electron transport, as well as providing a mechanically robust support for the CL. The gas diffusion in the GDL can be estimated by Fick’s law where the effective diffusion coefficient of gaseous species is used. There are many models in the literature based on correlations defining the effective diffusion coefficients through GDLs. Some of these models were originally derived to estimate the transport properties of a porous media composed of spherical particles, e.g. Bruggeman approximation and effective medium approximation. Inherently, such models tend to result to more inaccurate outcomes compared to the models which assume the GDL structure as cylindrical carbon fibers, i.e. the diffusion model based on percolation theory. The percolation theory model considers GDL as a medium composed of freely overlapping fibers oriented in different directions. However, there are several models available in the literature with less simplifying assumptions in GDL structure. The pore network model (PNM) reconstruct the porous media using topology and size information extracted from high resolution tomographic patterns. Also CFD based models can even investigate the actual GDL structure and reconstruct the 3D stochastic porous medium microstructure. These models combine pore-scale model with CFD approaches, e.g. lattice Boltzmann method (LBM) or direct numerical simulation (DNS). This study compares the available models for dry gas diffusion in GDL with experimental data acquired from symmetrical modified Loschmidt cell (SMLC). The SMLC is employed to measure the effective diffusion coefficient of oxygen passing through GDL samples, i.e. SGL SIGRACET 24BA, 24 BC, 25BA, 25BC and TGP-H-060. The SMLC result for effective diffusion coefficient in TGP-H-060 has less than 2% difference with the available data in the literature for this type of GDL. In order to evaluate the accuracy of effective medium models and percolation theory model, the experimental data for the above-mentioned GDLs is compared with the predictions of these models. The porosity of GDL samples are in the valid range of diffusion models. The diffusion models based on the effective medium approximation have the greater difference with SMLC data in compare with the percolation theory model. The model’s predictions are the worst for the GDLs with microporous layer (MPL), i.e. SIGRACET 24 BC and 25BC. Since the MPL imposes an extra resistance to gas diffusion which is not considered in any GDL diffusion models. The least error in model’s outcome is 30% which associates to the effective diffusion coefficient predicted by percolation theory model for SIGRACET 25BA.

Gas diffusion layer (GDL) is a vital component in proton exchange membrane fuel cells (PEMFC) due its main functions to conduct electrons and heat between the adjacent fuel cell components, provide preferential pathways for product water removal and to provide uniform reactant gas flow distribution to the electrode surface. Because of the anisotropic GDL microstructure, the transport properties vary in the through-plane and in-plane direction. Furthermore, during fuel cell stack assembly pressures exerted on the flowfield land compress the GDL under land cause changes of the GDL microstructure. While moderate compression increases GDL thermal conductivity due to increased fiber-fiber contacts, excessive compression may impede diffusive and liquid water transport due to loss of GDL pore volume. Detailed knowledge of how thermal conductivity is affected by the anisotropic nature of gas diffusion layers under compression is imperative in order to provide a better understanding on how thermal gradients influence two-phase transport during PEMFC operation. Previous research efforts have focused on steady-state methods for measuring effective through-plane GDL thermal conductivity [1][2][3][4] and effective in-plane GDL thermal conductivity [5][6] but to the best of our knowledge no studies have been conducted to measure effective in-plane GDL thermal conductivity for a variety of different GDL types under compression. This study attempts to fill that gap by using specially designed in-house tools to characterize the influence of GDL anisotropy on effective thermal conductivity as a function compression for different GDL types. Furthermore, a comprehensive ex-situ mechanical study is conducted to characterize the compliance matrix for different GDL types. Early results indicate a highly non-linear compressive behaviour in the GDL through-plane direction with large variations for the different GDL types. Moreover, the flexural modulus is found to be highly anisotropic where stiffness in the GDL machine direction (MD) is consistently larger compared to stiffness in GDL cross machine direction (CMD). This work will provide a foundation for a numerical study to couple an anisotropic GDL structural model with a non-isothermal two-phase model to investigate the effects of inhomogenous compression on two-phase transport. Keywords: GDL, PEMFC, ex-situ, anisotropy, modulus, microstructure, mechanical, compression, characterization, MD, CMD, through-plane, in-plane, thermal conductivity [1] G. Karimi, X. Li, P. Teertstra, Electrochim. Acta (2010). [2] R. Bock, A.D. Shum, X. Xiao, H. Karoliussen, F. Seland, I. V. Zenyuk, O.S. Burheim, J. Electrochem. Soc. 165 (2018) F514–F525. [3] G. Unsworth, N. Zamel, X. Li, Int. J. Hydrogen Energy (2012). [4] E. Sadeghi, N. Djilali, M. Bahrami, J. Power Sources (2011). [5] E. Sadeghi, N. Djilali, M. Bahrami, J. Power Sources (2011). [6] N. Alhazmi, D.B. Ingham, M.S. Ismail, K.J. Hughes, L. Ma, M. Pourkashanian, Int. J. Hydrogen Energy (2013).

Proton exchange membrane fuel cells (PEMFC) are an essential component of net zero emission scenarios by the International Energy Agency (IEA), most prominent in the heavy-duty transportation sector.[1-2] During operation, the PEMFC is subject to different operating conditions, particularly wet conditions where liquid water removal is crucial. It was observed that a microporous layer (MPL), commonly consisting of a carbon component (e.g. carbon black, carbon fibers) and a hydrophobic binder (e.g. PTFE), placed at the interface of the catalyst layer (CL) and the gas diffusion layer substrate (GDL-S), has a large impact on the water removal properties. Among other advantages, the addition of an MPL can guide the localization of water clusters in the GDL.[3] However, if interfaces exhibit large interfacial gaps, as was demonstrated for the CL/MPL interface,[4] liquid water can accumulate in the large openings, thereby creating a mass transport barrier. Seeking to understand the importance of interfaces, which can either guide water formation or create obstacles, this study further investigates the MPL/GDL-S interface. We created an intruding MPL by pressing the MPL slurry into the GDL-S using mechanical force (further on referred to as “intruded-GDL”) and compared it to a GDL, where the MPL sits quasi on top (further on referred to as “sheet-GDL”). Figure 1a shows a cross-sectional scanning electron microscopy (SEM image) of the sheet-GDL, while Figure 1b shows an intruded-GDL. The boundaries between the MPL material and the GDL-S are marked in red. The MPL/GDL-S interface of the sheet-GDL is relatively flat, following only the surface contour of the GDL-S, while the MPL/GDL-S interface of the intruded-GDL is pressed into the GDL-S and locally penetrates deeper into the GDL-S. It is also visible that the penetration into the GDL-S is inhomogeneous. We characterized the altered morphology using SEM (see Figure 1), mercury intrusion porosimetry (MIP), and x-ray tomographic microscopy (XTM). We found that the MPL of the intruded-MPL intrudes significantly into the GDL-S and preferably fills the larger pores of the GDL-S. Both types of GDLs were subject to single-cell fuel cell testing under various operating conditions. We found that the intruding MPL poses an additional oxygen transport resistance at dry conditions compared to the sheet-GDL. Under conditions where liquid water formation can be expected, the intruded-GDL starts to have an advantage compared to the sheet-GDL. From the data obtained in this study, a delicate interplay between the additional dry transport resistance, the missing macropores that were filled with MPL material, and the guided water removal properties can be deduced. We can derive an improved water removal mechanism for the intruded-GDL as a cause of the structural changes, which can serve as a guideline to improve GDL design parameters. References [1] IEA, Net Zero by 2050 2021,https://www.iea.org/reports/net-zero-by-2050. [2] D. A. Cullen, K. C. Neyerlin, R. K. Ahluwalia, R. Mukundan, K. L. More, R. L. Borup, A. Z. Weber, D. J. Myers, A. Kusoglu, Nat. Energy 2021, 6, 462-474. [3] J. T. Gostick, M. A. Ioannidis, M. W. Fowler, M. D. Pritzker, Electrochem. commun. 2009, 11, 576-579. [4] I. V. Zenyuk, E. C. Kumbur, S. Litster, J. Power Sources 2013, 241, 379-387. Acknowledgements We gratefully acknowledge funding from the Swiss National Science Foundation under the Sinergia grant number 180335. Figure 1 . SEM cross-sectional images different GDL configurations: a) a sheet-GDL; b) an intruded-GDL. The contours of the MPL material is marked with red lines. The MPL of the sheet-GDL is situated on top of the GDL-S, following the GDL-S surface contour, while the MPL of the intruded-GDL intrudes into larger pores of the GDL-S in an inhomogeneous manner. Figure 1

The gas diffusion layer (GDL) plays an important role in the mass transfer process during proton exchange membrane fuel cell (PEMFC) operation. However, the GDL porosity distribution, which has often been ignored in the previous works, influences the mass transfer significantly. In this paper, a 2D lattice Boltzmann method model is employed to simulate the liquid water transport process in the real GDL (considered porosity distribution) and the ideal GDL (ignore porous distribution), respectively. It was found that the liquid water transport in the real GDL will be significantly affected by the local low porosity area. In the real GDL, a liquid water saturation threshold can be noticed when the contact angle is about 118°. The GDL porosity distribution shows a stronger influence on liquid dynamic than hydrophobicity, which needs to be considered in future GDL modelling and design.

Polymer electrolyte water electrolyzers (PEMWEs) are a promising technology for the storage of energy from intermittent renewable sources such as wind and solar. PEMWEs split water into hydrogen and oxygen electrochemically. Under typical operating conditions, the hydrogen evolution reaction (HER) in the cathode is not limited by reactant transport, since it is supplied by the rapid transport of protons from the polymer electrolyte and electrons from the external circuit. There are very limited studies on the role of the cathode gas diffusion layer (GDL), typically a carbon-paper based layer. In this study, we investigated the effect of thickness, presence of a microporous layer, and wettability of the cathode GDL. Results show that cathode GDL properties have a significant effect on the performance of the PEMWE cells. Figure 1a shows the importance of the GDL thickness with the optimized GDL compression. The thickest GDL, MGL370 (i.e. 370µm thick ) has the best performance compared to MGL280 (280µm thick) and MGL190 (190µm thick). Compression of the GDL also affects the performance: when the compression is increased from 12% to 25% of the thickness, a performance loss is observed possibly due to damaged carbon fiber network and collapse the pores of the GDL (Figure 1b). Acknowledgment: Financial support from the US Department of Energy through the Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cells Technology Office is gratefully acknowledged. Figure 1

The gas diffusion layer (GDL) used in a PEFC is thicker than the electrode catalyst layer and electrolyte membrane. Thinning down the GDL can reduce gas diffusion resistance and volumetric power density of PEFC stacks. In this study, MPL/GDL is prepared by printing microporous layers (MPLs) on carbon meshes of several tens of micrometers thick as substrates for thin-layer GDLs. Through various current-voltage and overvoltage measurements and microstructural analysis of the cells using these thin-layer MPL/GDLs, cell performance has been improved, equivalent to that of the state of the MPL/GDL.

Hydrogen is converted to electric power by proton exchange membrane fuel cells (PEMFCs), which have received significant attention for transportation applications because of their high energy efficiency. In order to ensure the long-term stability, understanding about their long-term durability is essential because the operating performance deteriorates over time. Gas diffusion layers (GDLs) manage the transport of water generated from the CL during chemical reactions, and the degradation of the GDL significantly deteriorate the fuel cell performance. Compared to the fresh GDL, the water transport characteristics of GDL aged by inserting hydrogen peroxide solutions are investigated. The dynamic movement of the water meniscus inside the GDL is visualized using synchrotron X-ray imaging. Unlike the pristine GDL having snap-off patterns, water continuously transports through the degraded GDL representing the piston-like movement, and pressure fluctuations are not observed. This difference shows the change of the dominant local transport mechanisms due to GDL degradation. The temporal pressure variations are simultaneously measured, and the pressure and time at breakthrough (BT) are compared. The aged GDL exhibits a larger BT pressure and requires a longer time to achieve the first BT. Longer BT time in the degraded GDL can reflect a higher water saturation level. GDL degradation leads to the loss of polytetrafluoroethylene (PTFE) which is commonly treated to ensure efficient mass transport by restraining water clogging in the GDL pores due to the increase of hydrophobicity. Despite the reduction in hydrophobicity, The PTFE loss can increase BT pressure by reducing the pore size and the actual path length of the water flow. The increase in the BT time and BT pressure, as well as continuous transport, can disrupt fuel supply to chemical reaction sites, thereby deteriorating the PEMFC performance. This study provides a comprehensive understanding of the effect of GDL degradation on mass transport in PEMFCs. Figure 1

Gas diffusion layers (GDLs) play a critical role in anion exchange membrane fuel cell (AEMFC) water management. In this work, the effect of GDL thickness on the cell performance of the AEMFC was experimentally investigated. Three GDLs with different thicknesses of 120, 260, and 310 µm (denoted as GDL-120, GDL-260, and GDL-310, respectively) were prepared and tested in a single H2/O2 AEMFC. The experimental results showed that the GDL-260 employed in both anode and cathode electrodes exhibited the best cell performance. There was a small difference in cell performance for GDL-260 and GDL-310, while water flooding was observed in the case of using GDL-120 operated at current densities greater than 1100 mA cm−2. In addition, it was found that the GDL thickness had more sensitivity to the AEMFC performance as used in the anode electrode rather than in the cathode electrode, indicating that water removal at the anode was more challenging than water supply at the cathode. The strategy of water management in the anode should be different from that in the cathode. These findings can provide a further understanding of the role of GDLs in the water management of AEMFCs.

<abstract> <p>The gas diffusion layer (GDL) in the fuel cell has been made from carbon dispersion electrochemically deposited from binchotan. We prepared GDL by spraying the ink on the surface of the conductive paper. The carbon was then characterized by its crystallography, surface functional groups and size by x-ray diffraction (XRD), FT-IR and PSA instrumentations. Cyclic voltammetry and impedance spectroscopy tests were applied to study the GDL electrochemical characters. Buble drop tests were used to obtain contact angles representing the hydrophobicity of the layer. The electrodeposition/oxidation of binchotan derived carbon dispersion has a crystalline phase in its dot structure. According to particle size analysis, carbon dispersion has an average particle size diameter of 176.7 nm, a range of 64.5–655.8 nm, and a polydispersity index was 0.138. The Nyquist plot revealed that the processes in the GDL matrices as the plot consist of two types of structures, i.e., semicircular curves and vertical (sloping) lines. The GDL electrical conductivity of Vulcan and carbon dots were 0.053 and 0.039 mho cm^-1. The contact angle between conductive paper and water was 150.27°; between the gas diffusion layer and carbon Vulcan was 123.28°, and between the gas diffusion layer and carbon dispersion was 95.31°. The surface of the GDL with Vulcan is more hydrophobic than that made with carbon dispersion. In other words, the GDL with carbon dispersion is closer to hydrophilic properties. The results show that the carbon can support the gas diffusion layer for hydrophobic and hydrophilic conditions.</p> </abstract>

Les piles à combustible PEMFC représentent l'avenir des véhicules électriques lourds. L'amélioration des performances, des coûts et de la durabilité de ses composants constitue les objectifs clé pour cette technologie. La couche de diffusion des gaz (GDL) joue un rôle essentiel dans les performances de la PEMFC. En effet, elle assure le transport des fluides, les conductivités électriques et thermiques, et réduit le noyage de la cathode tout en maintenant la membrane hydratée [1].La fabrication et la caractérisation des GDL électrofilées (eGDL) sont étudiées. L'électrofilage permet de créer des fibres de carbone et des pores de l'ordre de quelques centaines de nanomètres. C'est deux ordres de grandeur plus petits que la taille des fibres et des pores des GDL commerciales. L'électrofilage a récemment été utilisé pour concevoir des GDL pour les PEMFC [2],[3]. La polyvalence de cette technique innovante est exploitée pour produire des eGDL avec des microstructures (taille de fibres, taille de pores) contrôlées [4]. L'imagerie haute résolution (tomographie à rayons X en synchrotron, Fib-Sem) est utilisée pour analyser la microstructure des GDL électrofilées et commerciales. Une méthode de segmentation machine learning est utilisée pour séparer les différentes phases solides des GDL commerciales (phase fibre hydrophile et phase liant/PTFE hydrophobe). Des simulations d'intrusion d'eau sont réalisées en tenant compte de la mouillabilité mixte des différentes phases. Une caractérisation détaillée des propriétés de transport des fluides (diffusion, tortuosité, perméabilité aux gaz et aux liquides, pression capillaire) est menée à partir des structures 3D [5]. La dépendance à l'intrusion simulée d'eau liquide et à la compression est étudiée. Des relations entre les propriétés de transport et les paramètres microstructuraux sont établies, évaluant l'applicabilité des modèles classiques tels que Bruggeman et Karman-Kozeny. Enfin, les résultats sont reliés avec les performances électrochimiques réelles de la GDL en effectuant des essais sur des piles à combustible. La microstructure des eGDL est optimisée en ajustant les paramètres de fabrication pour améliorer les propriétés de transport des fluides et les performances. Des performances proches de celles des GDL commerciales (<10% de différence) sont obtenues avec des eGDL sans liant et sans PTFE, réduisant ainsi la complexité de la GDL. Cette thèse permet de mieux comprendre les relations entre la microstructure, les propriétés de transport des fluides et les performances de la GDL.[1] A. Ozden, S. Shahgaldi, X. Li, and F. Hamdullahpur, Progress in Energy and Combustion Science, vol. 74, pp. 50–102, Sep. 2019, doi: 10.1016/j.pecs.2019.05.002.[2] S. Chevalier, N. Lavielle, B. D. Hatton, and A. Bazylak, Journal of Power Sources, vol. 352, pp. 272–280, Jun. 2017, doi: 10.1016/j.jpowsour.2017.03.098.[3] G. Ren, Z. Qu, X. Wang, and G. Zhang, International Journal of Hydrogen Energy, p. S0360319923009254, Mar. 2023, doi: 10.1016/j.ijhydene.2023.02.093.[4] J. Xue, T. Wu, Y. Dai, and Y. Xia, Chem. Rev., vol. 119, no. 8, pp. 5298–5415, Apr. 2019, doi: 10.1021/acs.chemrev.8b00593.[5] J. Becker, R. Flückiger, M. Reum, F. N. Büchi, F. Marone, and M. Stampanoni, , J. Electrochem. Soc., vol. 156, no. 10, p. B1175, 2009, doi: 10.1149/1.3176876
PEM fuel cells represent the future of heavy electric vehicles. Improving the performance, cost and durability of its components constitutes key objectives for this technology. The gas diffusion layer (GDL) plays a critical role in fuel cell performance. Indeed, it ensures fluid transport, provides electrical and thermal conductivities, and must prevent cathode flooding while keeping the membrane well hydrated [1].The manufacture and characterization of electrospun GDL (eGDL) is investigated. Electrospinning allows for the creation of carbon fibers and pores in the range of hundreds of nanometers. This is two orders of magnitude smaller than the fiber and pore sizes of commercial GDL. Electrospinning has recently been used to design tailored porous media for PEMFC [2], [3]. The versatility of this innovative technique is exploited to produce eGDL with controlled microstructures, varying porosity, fiber and pore sizes [4]. High resolution imaging (synchrotron X-Ray tomography, FIB-SEM) is employed to analyse the microstructure of electrospun and commercial GDL. An advanced segmentation method by machine learning is used to separate the different solid phases of commercial GDL (hydrophilic fiber phase and hydrophobic binder/PTFE phase). A detailed characterization of fluid transport properties (diffusion, tortuosity, gas and liquid permeability, capillary pressure) is investigated from segmented 3D structures [5]. Water intrusion simulations are carried out, taking into account the mixed wettability of the different phases. The dependence on simulated liquid water intrusion and of compression is explored. Relationships between transport properties and microstructural parameters are established, evaluating the applicability of classical models such as Bruggeman and Karman-Kozeny. Finally, the results are related to the actual electrochemical performance of GDL by performing fuel cell tests. The microstructure of eGDL is optimized by adjusting the manufacturing parameters for improved fluid transport properties and performance. Performance close to those of commercial GDL (<10% difference) are obtained with binder-free and PTFE-free eGDL, thus reducing the complexity of the GDL. This thesis provides a better understanding of the relationships between microstructure, fluid transport properties and GDL performance.[1] A. Ozden, S. Shahgaldi, X. Li, and F. Hamdullahpur, Progress in Energy and Combustion Science, vol. 74, pp. 50–102, Sep. 2019, doi: 10.1016/j.pecs.2019.05.002.[2] S. Chevalier, N. Lavielle, B. D. Hatton, and A. Bazylak, Journal of Power Sources, vol. 352, pp. 272–280, Jun. 2017, doi: 10.1016/j.jpowsour.2017.03.098.[3] G. Ren, Z. Qu, X. Wang, and G. Zhang, International Journal of Hydrogen Energy, p. S0360319923009254, Mar. 2023, doi: 10.1016/j.ijhydene.2023.02.093.[4] J. Xue, T. Wu, Y. Dai, and Y. Xia, Chem. Rev., vol. 119, no. 8, pp. 5298–5415, Apr. 2019, doi: 10.1021/acs.chemrev.8b00593.[5] J. Becker, R. Flückiger, M. Reum, F. N. Büchi, F. Marone, and M. Stampanoni, , J. Electrochem. Soc., vol. 156, no. 10, p. B1175, 2009, doi: 10.1149/1.3176876

L'objectif de cette thèse a consisté à étudier des procédés de fabrication de couches de diffusion de gaz (GDL) en silicium poreux appliqués à l'intégration de micropiles à combustible de type PEMFC sur plaquette de silicium. Deux types de couches ont été étudiés : sur surface plane (2D) et sur surface texturée (3D). Les couches de diffusion de gaz ont été réalisées par l'anodisation de silicium de type N fortement résistif. Une localisation des motifs poreux a été obtenue par ouverture d'un masque en polysilicium sur oxyde thermique de silicium. Seules les GDL 2D entièrement macroporeuses assuraient un débit d'hydrogène compatible avec les objectifs de fabrication d'une micropile prototype. Le prototype a permis de valider la compabilité de la couche de diffusion de gaz avec les étapes d'empilement des couches actives constitutive de la micropile. Son fonctionnement nous a permis d'atteindre une densité de puissance de 250 mW/cm²
This thesis work deals with porous silicon gas diffusion layer (GDL) fabrication process. The aim was to integrate this GDL into proton exchange membrane micro fuel cells (PEMFC). Consequently, the GDL must be localized in specific wafer areas. We have also developed 2D and 3D structures. To produce a GDL, we have anodized low doped N type silicon subrates. thus, we have fabricated macroporous GDL and double layer structures made up of a mesaporous layer on a macroporous one. Patterning of the GDL has been obtained through a hard mask (polysilicon on top of a silicon oxide layer) or using a localized doping. We have concluded this work by achieving micro fuel cell prototypes with macroporous silicon gas diffusion layers. After validation of micro PEMFC active layer mechanical stacking, we have measured a maximum power density of about 250 mW/cm²

Dans ce travail, nous nous intéressons aux précurseurs de zircone synthétisés par voie sol-gel: gel,xérogel,couche mince et aérogel. L'objectif est de préciser le rôle spécifique des différents états d'agrégation des particules élémentaires constituant ces précurseurs sur l'évolution de leur microstructure au cours de traitements thermiques à basse température. La technique de caractérisation majoritairement utilisée est la diffusion centrale des rayons X. Dans le cas des couches minces, la géométrie du montage expérimental a été adaptée au cas de l'incidence rasante et un appareillage original de réflectrométrie des rayons X,permettant de mesurer leur épaisseur et leur densité,a également été mis au point. Le sol précurseur de zircone est élaboré dans un système n-propoxyde de zirconium,acétylacétone, n-propanol et eau. Pour la composition choisie,la nature colloi͏̈dale du sol est clairement demontrée. Au cours de la gélification, le réseau solide s'établit par un mécanisme d'agrégation amas-amas limité par la diffusion et présente une microstructure fractale. Au cours d'un séchage par étuvage,cette microstructure s'effondre. Le xérogel est alors constitué d'un empilement compact des particules élémentaires du gel. Lors de recuits isothermes à basse température,il cristallise dans la phase quadralique de la zircone. Les cristaux,nanométriques,sont spacialement ordonnés et leur distribution en taille est relativement étroite. Leur croissance est contrôlée par un mécanisme de diffusion de surface. Les films minces sont réalisés par trempage d'un substrat monocristallin d'alumine dans le sol précurseur de zircone. Ils se forment par concentration de ses particules élémentaires à la surface du substrat. Leur évolution microstructurale, lors de recuits isothermes à faible température, est en tout point similaire à celle du xérogel massif et la présence de l'interface couche-substrat ne semble pas jouer un rôle prépondérant
In this work, we are interested in zirconia precursors synthesised by the sol gel method : gel, xerogel, thin film and aerogel. The objective is to precise the specific role of the various states of aggregation of the elementary particles constituting these precursors on the evolution of their microstructure during a low temperature thermal processing

A new type of fuel cell architecture, the fuel cell ribbon, is presented. The fuel cell ribbon architecture relies on the gas diffusion layer (GDL) to conduct electrical current in-plane to adjacent cells or collector terminals. The potential advantages of the fuel cell ribbon architecture with respect to conventional fuel cell stacks include reduced manufacturing costs, reduced weight, reduced volume, and reduced component cost. The critical component of fuel cell ribbon assemblies, the gas diffusion media, is investigated herein. Analytical models which focus on the electrical loses within the gas diffusion media of the novel architecture are developed. The materials and treatments necessary to fabricate novel gas diffusion media for fuel cell ribbon assemblies are presented. Experimental results for the novel gas diffusion media of are also presented. One dimensional and two dimensional analytical models were developed for the fuel cell ribbon. The models presented in this work focus on the losses associated with the transport of the electrons in fuel cell ribbon assemblies, rather than the complex system of equations that governs the rate of electron production. The 1-D model indicated that the GDL used in ribbon cells must exhibit an in-plane resistance which is approximately an order of magnitude lower than the resistance of gas diffusion media typically used in conventional fuel cells. A 2-D model was developed with which a parametric study of GDL properties and ribbon cell dimensions was performed. The parametric study indicated that ribbon cells of useful size can be constructed using novel diffusion media that offer reduced resistivity, and that the ribbon cells can produce as much as 80-85% of the power density produced in a conventional fuel cell. Novel gas diffusion media for fuel cell ribbons that have the necessary characteristics suggested by the analytical study were developed.. Properties and performance for a commercially available gas diffusion media, ELAT, were measured as a reference for the novel media developed. The increased thickness PAN (ITPN) series diffusion media was constructed of PAN based fibers exhibiting similar resistive properties to the fibers used in ELAT. The ITPN series of materials were woven in a manner which made them approximately twice the thickness of ELAT, effectively reducing their in-plane resistance to half the resistance exhibited by ELAT. The coarsely woven pitch (CWPT) series of materials were constructed in a manner which yielded a similar number of fibers in the plane of the material to ELAT and a similar material thickness to ELAT, but the fibers used were mesophase pitch based fibers which exhibit a resistivity of approximately one-tenth the resistivity of the fibers used to make the ELAT and ITPN materials. The reduction in fiber resistivity led to the CWPT material having an in-plane resistance an order of magnitude lower than ELAT. The widely used ELAT material exhibited an in-plane resistance of 0.39 Ω/sq., a through-plane area specific resistance of 0.007 Ω-cm2, and a Darcy permeability coefficient of 8.1 Darcys. The novel diffusion materials exhibited in-plane resistances in the range of 0.18-0.036 Ω/sq., through-plane area specific resistances in the range of 0.017-0.013 Ω-cm2, and Darcy permeability coefficients in the range of 30-150 Darcys. Experiments were performed to validate the analytical model and to prove the feasibility of fuel cell ribbon concept. When the novel gas diffusers were adhered to a catalyzed membrane and tested in a ribbon test assembly utilizing serpentine flow channels and in-plane current collection, a range of performance was achieved between 0.28-0.4 A/cm2 at a cell output potential of 0.5 V. In contrast, when ELAT was adhered to a catalyzed membrane and tested in the fixture requiring in-plane conduction, a current density of 0.21 A/cm2 was achieved at 0.5 V. Additionally, the 2-D finite element model was used to predict the performance of a ribbon cell based on the cells performance when a conventional method of through-plane conduction was utilized. The agreement between the experimental data and the model predictions was very good for the ELAT and ITPN materials, whereas the predictions for the CWPT materials showed more significant deviation which was likely due to mass transport and contact resistance effects.
Master of Science

The gas diffusion layer (GDL) is one of the key components in a polymer electrolyte membrane (PEM) fuel cell. It performs several functions including the transport of reactant gases and product water to and from the catalyst layer, conduction of both electrons and heat produced in the catalyst layer, as well as mechanical support for the membrane. The overarching goal of this work is to thoroughly examine the GDL structure and properties for use in PEM fuel cells, and more specifically, to determine how to characterize the GDL experimentally ex-situ, to understand its performance in-situ, and to relate theory to performance through controlled experimentation. Thus, the impact of readily measured effective water vapor diffusivity on the performance of the GDL is investigated and shown to correlate to the wet limiting current density, as a surrogate of the oxygen diffusivity to which it is more directly related. The influence of microporous layer (MPL) design and construction on the fuel cell performance is studied and recommendations are made for optimal MPL designs for different operating conditions. A method for modifying the PTFE (Teflon) distribution within the GDL is proposed and the impact of distribution of PTFE in the GDL on fuel cell performance is studied. A method for characterizing the surface roughness of the GDL is developed and the impact of surface roughness on various ex-situ GDL properties is investigated. Finally, a detailed analysis of the physical structure and permeability of the GDL is provided and a theoretical model is proposed to predict both dry and wet gas flow within a GDL based on mercury intrusion porosimetry and porometry data. It is hoped that this work will contribute to an improved understanding of the functioning and structure of the GDL and hence advance PEM fuel cell technology.

Due to escalating energy costs and limited fossil fuel resources, much attention has been given to polymer electrolyte membrane (PEM) fuel cells. Gas diffusion layers (GDLs) play a vital role in a fuel cell such as (1) water removal, (2) cooling, (3) structural backing, (4) electrical conduction and (5) transporting gases towards the active catalyst sites where the reactions take place. The power density of a PEM fuel cell in part is dependent upon how uniform the gases are distributed to the active sites. To this end, research is being conducted to understand the mechanisms that influence gas distribution across the fuel cell. Emerging PEM fuel cell designs have shown that higher power density can be achieved; however this requires significant changes to existing components, particularly the GDL. For instance, some emerging concepts require higher through-plane gas permeability than in-plane gas permeability (i.e., anisotropic resistance) which is contrary to conventional GDLs (e.g., carbon paper and carbon cloth), to obtain a uniform gas distribution across the active sites. This is the foundation on which this thesis is centered. A numerical study is conducted in order to investigate the effect of the gas permeability profile on the expected current density in the catalyst layer. An experimental study is done to characterize the effects of the weave structure on gas permeability in woven GDLs. Numerical simulations are developed using Fluent version 6.3.26 and COMSOL Multiphysics version 3.5 to create an anisotropic resistance profile in the unconventional GDL, while maintaining similar performance to conventional GDL designs. The effects of (1) changing the permeability profile in the in-plane and through-plane direction, (2) changing the thickness of the unconventional GDL and (3) changing the gas stoichiometry on the current density and pressure drop through the unconventional GDL are investigated. It is found that the permeability profile and thickness of the unconventional GDL have a minimal effect on the average current density and current density distribution. As a tradeoff, an unconventional GDL with a lower permeability will exhibit a higher pressure drop. Once the fuel cell has a sufficient amount of oxygen to sustain reactions, the gas stoichiometry has a minimal effect on increases in performance. Woven GDL samples with varying tightness and weave patterns are made on a hand loom, and their in-plane and through-plane permeability are measured using in-house test equipment. The porosity of the samples is measured using mercury intrusion porosimetry. It is found that the in-plane permeability is higher than the through-plane permeability for all weave patterns tested, except for the twill weave with 8 tows/cm in the warp direction and 4 tows/cm in the weft direction, which exhibited a through-plane permeability which was 20% higher than the in-plane permeability. It is also concluded that the permeability of twill woven fabrics is higher than the permeability of plain woven fabrics, and that the percentage of macropores, ranging in size from 50-400 µm, is a driving force in determining the through-plane permeability of a woven GDL. From these studies, it was found that the graduated permeability profile in the unconventional GDL had a minimal effect on gas flow. However, a graduated permeability may have an impact on liquid water transport. In addition, it was found that graduating the catalyst loading, thereby employing a non-uniform catalyst loading has a greater effect on creating a uniform current density than graduating the permeability profile.

Nous avons réalisé des mesures expérimentales de diffusion résonante de rayon X sur des molécules chlorées isolées en phase gazeuse (HCl, CH3Cl). Nous avons utilisé le rayonnement synchrotron dans le domaine des rayons X ‘tendres’ (1-10 keV) comme source d’excitation. L’intérêt de cette gamme d’énergie réside dans la durée de vie femtoseconde, voir sub-femtoseconde de la lacune créée après absorption d’un photon. La spectroscopie de diffusion des rayons X permet de mettre à profit ce temps caractéristique, introduit dans l’état intermédiaire, pour sonder dans cette échelle de temps, la dynamique nucléaire. Nous avons mesuré à la fois l’émission Kα et Kβ au seuil Cl K de ces molécules chlorées. Le comportement de l’émission Kα en fonction de l’énergie d’excitation nous apporte des informations sur la topologie des surfaces d’énergie potentielle. La forme de l’émission Kβ en fonction de l’énergie d’excitation permet de sonder plus particulièrement la dynamique nucléaire ayant lieu dans l’état intermédiaire. Cette émission permet également d’accéder à la variation de la section efficace élastique en fonction de l’énergie d’excitation montrant des profils caractéristique d’interférence. Tous ces résultats sont analysés dans le cadre du formalisme de la diffusion résonante des rayons X où des calculs de DFT ont été menés en collaboration.

Les objets électromagnétiques sont conçus en considérant des matériaux aux propriétés radio-électriques (permittivité, perméabilité) homogènes. Néanmoins, lors de leur réalisation les matériaux réels peuvent présenter des fluctuations de ces propriétés. Ce travail porte sur la mise au point d'outils capables d'estimer le champ diffusé produit par les fluctuations. Trois méthodes ont été mises au point : EMFORS, ABE et RECY pour la détermination du champ diffusé par des fluctuations de permittivité et de perméabilité. La modélisation de la contribution des fluctuations de perméabilité est une avancée significative. En effet, il n'existait pas d'outil traitant ce problème dans toute sa généralité pour estimer le champ diffusé par cette fluctuation. L'absence de magnétisme aux fréquences des ondes optiques en est la principale raison.La méthode RECY est une méthode qui permet d'estimer à l'aide du principe de réciprocité le champ diffusé dans un objet quelconque à partir de la simple connaissance du champ dans l'objet sans défaut et de la fluctuation. Cette méthode permet une fois le calcul du champ idéal effectué par une méthode quelconque (analytique ou numérique) de calculer le champ diffusé de n'importe quelle forme de fluctuation. Nous avons appliqué RECY à des structures comme un réseau simple, une structure industrielle et aux cristaux photoniques
Electromagnetic objects are designed by considering homogeneous materials properties (permittivity, permeability). However, during their realization real materials may present fluctuations of their properties. This work focuses on the development of tools able to estimate scattered fields produced by fluctuations. Three methods have been developed: EMFORS, ABE and RECY for the determination of the scattered field by fluctuations of permittivity and permeability. Taking into account permeability fluctuations is a significant advance. Indeed, there was no tool to estimate the scattered field by such a fluctuation, due to the absence of magnetic properties at optical frequencies.The RECY method is a method which allows to estimate the field in an object using the principle of reciprocity from the knowledge of the field in the object without defect and of the fluctuation function. This method allows, once the ideal field calculated by any method (analytic or digital), to obtain the scattered field from any structure.We applied RECY for structures such as elementary gratings, an industrial structure and photonic crystals

AbstractThe fertility levels of developing countries correlate with many socio-economic variables including girls’ or women’s education, infant and child mortality, GDP/capita, and percent urban. To determine whether these correlations are causal or simply due to collinearity we rely on multivariate fixed effect regression analyses. The results identify women’s education as the most important determinant of fertility, which is consistent with past studies. Next, we examine the relationship between education and fertility over the course of transitions from 1960 and 2015 in individual developing countries. Instead of finding continuous relationships during the transitions, several puzzling anomalies appear. In the pre-transition phase, fertility is unresponsive to rising education resulting in delays in the onset of transition. Once a few countries in a region enter the transition, other countries follow sooner than expected and over time the onset of the transition occurs at ever lower levels of education. Moreover, once a transition is underway, fertility in many countries declines more rapidly than can plausibly be expected from rising education levels alone. To explain these anomalies, we rely on several concepts that have been neglected in conventional demographic theories: diffusion processes, social norms, and family planning programs.

The structure of porous media is composed of skeleton particles and pores. Its micro-pores and solid skeleton characteristics lead to the capillary fingering movement of fluid in its porous media driven by capillary pressure. Currently, the methods of constructing porous media are mainly random construction and multi-scale imaging construction. The porous structure constructed by these two methods can show the real microstructure characteristics. The research on multiphase flow in microporous structure mainly includes VOF, MC, LBM, and other methods. In this chapter, taking the classic porous structure of polymer electrolyte membrane (PEM) fuel cell gas diffusion layer (GDL) as an example, GDL porous microstructure is constructed through random algorithm, and multiphase LBM is used to study two-phase flow in porous media to explore the relationship between porous structure characteristics and multiphase flow transport.

The mass transfer characteristics of the gas diffusion layer (GDL) in a polymer electrolyte fuel cell (PEFC) are closely related to the performance. In this study, the oxygen diffusivity of paper and cloth type porous media, which are generally used as GDLs, were measured with respect to liquid water content, using experimental apparatus consisting of an oxygen sensor based on a galvanic battery. Paper type porous media, both non treated and hydrophilic treated, and the cloth type porous media with non treated surface were used as GDL specimens. The porosity of both specimens was almost the same, but the representative pore diameter of the cloth type GDL was approximately three times larger than that of paper type GDL. Two methods were utilized to impregnate liquid water into the porous GDL media to realize different water distributions in the specimens at the initial state; vacuum impregnation and moist air condensation impregnation. The oxygen diffusivities of the specimens were measured to clarify the influence of the two impregnation methods on the oxygen diffusion characteristics. Moreover, the relation between the measurement of oxygen diffusivity and the visualization of the liquid water distribution by using Neutron Radiography [Tasaki et al. (2007)] was investigated for the paper and cloth type GDLs. The oxygen diffusivity in the paper type porous media decreased precipitously with increasing water saturation by the vacuum impregnation method, whereas the diffusivity decrease was relatively small when impregnated by the moist air condensation method. For the cloth type porous media with weaving threads, oxygen diffusion characteristics were independent of the water impregnation method. Thus, the porous medium’s microstructure plays an important role in determining diffusion characteristics, especially in the presence of liquid water.

A radial flow device was fabricated to experimentally characterize the in-plane flow behavior of gas diffusion layers (GDL). Radial flow of gas and liquid through the GDL result in the same permeability values. Finally, four types of commercially available GDL are characterized at various levels of compression.

In the present study, a three dimensional pore network, consisting of spherical pores and cylindrical throats, is developed to simulate the oxygen diffusion and liquid water permeation in gas diffusion layer (GDL) in low-temperature fuel cell. Oxygen transport in the throats is described by Fick’s law and liquid water permeation in the network is simulated using percolation invasion algorithm. The effects of heterogeneity of GDL, connectivity of pores, and liquid water saturation on oxygen effective diffusivity are investigated respectively. The simulation results show that the GDL structure has a significant influence on the oxygen and water transport in the GDL. The oxygen effective diffusivity increases with increasing pore connectivity and decreasing heterogeneity. The shielding effect of large throats by smaller ones enhances with increasing heterogeneity of the network. Furthermore, the oxygen transportation is blocked in the presence of liquid water permeation. Thus the oxygen effective diffusivity drops significantly with increasing water saturation.

Thermal and water management is critical to fuel cell performance. It has been shown that gas diffusion layer (GDL) can impose the mass transport limit; for example, it can block the reactant transport to active layer when flooding occurs at high current density conditions. Micro porous layer (MPL) in conjunction with backing layer (BL) has been used as a GDL material and was shown to be effective for water management. To study the transport processes in GDL and MPL modified GDL, an analytical solution is derived current study for calculation of two-phase, multicomponent transport in GDL. Two models were considered, the unsaturated flow model (UFM) and the separate flow model (SFM). Comparison of the calculated saturation level and oxygen mass fraction shows that UFM calculation can underestimate, as well as overestimate the saturation and oxygen concentration. The SFM was used to study the effects due to GDL property variations. The calculation shows that increase in liquid water transport in an MPL modified GDL is due to the abrupt change of liquid water flow rate when a step change in porosity or permeability is imposed. The calculation further shows that particle size of around 1 μm would be a good choice for MPL as it results in higher oxygen concentration at active layer and lower saturation in GDL.

A three-dimensional, single-phase, isothermal numerical model of polymer electrolyte fuel cell (PEFC) is employed to investigate effects of lateral electron transport in gas diffusion layer (GDL) for the first time. An additional electron transport equation is solved in the catalyst and gas diffusion layers, and in the current collector. It is found that the lateral electronic resistance plays a critical role in determining the current distribution and cell performance. With reduced GDL thickness, the effect of the lateral electronic resistance becomes even stronger, because the cross-sectional area of GDL for lateral electron transport is smaller. Inclusion of GDL electron transport enables the thickness of GDL and widths of the gas channel and current collecting land to be optimized for better current distribution and cell performance. In addition, the present model enables: (1) direct incorporation of contact resistances emerging from GDL/catalyzed membrane and GDL/land interfaces in the solution process, (2) natural implementation of the total current as the more useful boundary condition than the cell voltage, and (3) stack modeling with cells connected in series and hence having the identical total current.

The flooding, especially in gas diffusion layer (GDL), is one of the critical issues to put PEMFC to practical use. However, the experimental data of the flooding in GDL is so insufficient that the optimization design to solve the flooding problem in GDL has not established until now. In this study we show a method to estimate the water saturation, namely the water droplet occupation for unit volume in GDL. We fabricated a simple interdigitated cell where the supply gas is enforced to flow under rib. This structure made it possible to capture the water droplet in GDL with the measurement of differential pressure through the cell. We operated the cell and measured the differential pressure, and estimated the water saturation with assuming that the flow in GDL is Darcy flow and that the GDL can be treated as sphere packed bed. In addition to deferential pressure measurement, we measured the ionic resistance in polymer electrolyte membrane by AC impedance method. We evaluated the effect of the water saturation on the decrease of cell voltage.

This paper reports our recent work on the stochastic-model-based reconstruction of the gas diffusion layer (GDL) of PEFCs and direct numerical simulation and presented the pore-level transport within GDLs of polymer electrolyte fuel cell (PEFC). The carbon-paper-based GDL is modeled as a stack of thin sections with each section described by planar 2D random line tessellations which are further dilated to three dimensions. The reconstruction of the GDL structure is based on given GDL data provided by scanning electron microscopy (SEM) images. Based on the stochastically constructed digital GDL, we further conduct the DNS of the coupled transport processes, including gas flow and species transport, electronic current conduction, and heat transfer. Results indicate remarkable distinction in tortuosities of gas diffusion passage and solid matrix. The numerical tool can be applied to investigate the GDL microstructure and internal pore-level transport in PEFCs.

In this work, thermal conductivities of gas diffusion layer (GDL) under controlled temperature, humidity and stress are measured. Additionally, we investigated the anisotropic thermal conductivity of GDLs. The experimental results showed that thermal conductivity of in-plane direction was much higher than that of trough-plane direction for all the samples that were measured. This result indicated thermal conductivity of GDLs to be strongly anisotropic since GDL is a highly porous material which contains large amount of air inside the GDL. Moreover, we found that thermal conductivity of GDL in the through-plane direction increased as the compression on the GDL was increased.

Despite tremendous progress in recent years, a pivotal performance limitation in PEM fuel cells manifests in terms of mass transport loss owing to liquid water transport and resulting flooding. A key contributor to the mass transport loss is the cathode gas diffusion layer (GDL) due to the blockage of available pore space by liquid water thus rendering hindered oxygen transport to the active reaction sites in the electrode. The GDL, typically a non-woven carbon paper or woven carbon cloth, thus plays an important role in the overall water management in PEM fuel cells. The underlying pore-morphology and the pore wetting characteristics have significant influence on the flooding dynamics in the GDL. Another important factor is the role of cell compression on the GDL microstructural change. In this work, we investigate the influence of GDL microstructure change under compression on the transport behavior. We will present an improved compression model based on the micro finite element approach. The compression of reconstructed GDL microstructures along with effective property estimation and transport characterization are elucidated.

The mechanism of liquid water removal, water vapor diffusion and oxygen diffusion in cathode side gas diffusion layer (GDL) of PEFC is studied by modeling the GDL as a hydrophobic flat plate with many straight holes with different diameters. As the results of the consideration using the model, following results are obtained. The spots where liquid water condensation is taken place between GDL-MEA gap are limited to the inlets of holes with larger diameters, and the condensed water is drained to air flow channel only through the larger holes. Other holes with smaller diameters are free of liquid water, and oxygen diffuses from the air flow channel to the catalyst surface through such holes. The reduction of output voltage of fuel cell due to the increase in the current density may be caused by the reduction of the oxygen concentration in GDL-MEA gap. The condensate tends to penetrate into larger holes instead of filling the gap of GDL and MEA.

1. Macroeconomic Summary In December, headline inflation (13.1%) and the average of the core inflation measures (10.3%) continued to trend upward, posting higher rates than those estimated by the Central Bank's technical staff and surpassing the market average. Inflation expectations for all terms exceeded the 3.0% target. In that month, every major group in the Consumer Price Index (CPI) registered higher-than-estimated increases, and the diffusion indicators continued to show generalized price hikes. Accumulated exchange rate pressures on prices, indexation to high inflation rates, and several food supply shocks would explain, in part, the acceleration in inflation. All of this is in a context of significant surplus demand, a tight labor market, and inflation expectations at different terms that exceed the 3.0% target. Compared to the October edition of the Monetary Policy Report, the forecast path for headline and core inflation (excluding food and regulated items: EFR) increased (Graphs 1.1 and 1.2), reflecting heightened accumulated exchange rate pressures, price indexation to a higher inflation rate (CPI and the producer price index: PPI), and the rise in labor costs attributed to a larger-than-estimated adjustment in the minimum wage. Nevertheless, headline inflation is expected to begin to ease by early 2023, although from a higher level than had been estimated in October. This would be supported initially by the slowdown forecast for the food CPI due to a high base of comparison, the end anticipated for the shocks that have affected the prices of these products, and the estimated improvement in external and domestic supply in this sector. In turn, the deterioration in real household income because of high inflation and the end of the effects of pent-up demand, plus tighter external and domestic financial conditions would contribute to diluting surplus demand in 2023 and reducing inflation. By the end of 2023, both headline and core (EFR) inflation would reach 8.7% and would be 3.5% and 3.8%, respectively, by December 2024. These forecasts are subject to a great deal of uncertainty, especially concerning the future behavior of international financial conditions, the evolution of the exchange rate, the pace of adjustment in domestic demand, the extent of indexation of nominal contracts, and the decisions taken regarding the domestic price of fuel and electricity. In the third quarter, economic activity surprised again on the upside and the growth projection for 2022 rose to 8.0% (previously 7.9%). However, it declined to 0.2% for 2023 (previously 0.5%). With this, surplus demand continues to be significant and is still expected to weaken during the current year. Annual economic growth in the third quarter (7.1 % SCA)1 was higher than estimated in October (6.4 % SCA), given stronger domestic demand specifically because of higher-than-expected investment. Private consumption fell from the high level witnessed a quarter earlier and net exports registered a more negative contribution than anticipated. For the fourth quarter, economic activity indicators suggest that gross domestic product (GDP) would have remained high and at a level similar to that observed in the third quarter, with an annual variation of 4.1%. Domestic demand would have slowed in annual terms, although at levels that would have remained above those for output, mainly because of considerable private consumption. Investment would have declined slightly to a value like the average observed in 2019. The real trade deficit would have decreased due to a drop in imports that was more pronounced than the estimated decline in exports. On the forecast horizon, consumption is expected to decline from current elevated levels, partly because of tighter domestic financial conditions and a deterioration in real income due to high inflation. Investment would also weaken and return to levels below those seen before the pandemic. In real terms, the trade deficit would narrow due to a lower momentum projection for domestic demand and higher cumulative real depreciation. In sum, economic growth for all of 2022, 2023, and 2024 would stand at 8.0%, 0.2% and 1.0%, respectively (Graph 1.3). Surplus demand remains high (as measured by the output gap) and is expected to decline in 2023 and could turn negative in 2024 (Graph 1.4). Although the macroeconomic forecast includes a marked slowdown in the economy, an even greater adjustment in domestic absorption cannot be ruled out due to the cumulative effects of tighter external and domestic financial conditions, among other reasons. These estimates continue to be subject to a high degree of uncertainty, which is associated with factors such as global political tensions, changes in international interest rates and their effects on external demand, global risk aversion, the effects of the approved tax reform, the possible impact of reforms announced for this year (pension, health, and labor reforms, among others), and future measures regarding hydrocarbon production. In 2022, the current account deficit would have been high (6.3 % of GDP), but it would be corrected significantly in 2023 (to 3.9 % of GDP) given the expected slowdown in domestic demand. Despite favorable terms of trade, the high external imbalance that would occur during 2022 would be largely due to domestic demand growth, cost pressures associated with high freight rates, higher external debt service payments, and good performance in terms of the profits of foreign companies.2 By 2023, the adjustment in domestic demand would be reflected in a smaller current account deficit especially due to fewer imports, a global moderation in prices and cost pressures, and a reduction in profits remitted abroad by companies with foreign direct investment (FDI) focused on the local market. Despite this anticipated correction in the external imbalance, its level as a percentage of GDP would remain high in the context of tight financial conditions. In the world's main economies, inflation forecasts and expectations point to a reduction by 2023, but at levels that still exceed their central banks' targets. The path anticipated for the Federal Reserve (Fed) interest rate increased and the forecast for global growth continues to be moderate. In the fourth quarter of 2022, logistics costs and international prices for some foods, oil and energy declined from elevated levels, bringing downward pressure to bear on global inflation. Meanwhile, the higher cost of financing, the loss of real income due to high levels of global inflation, and the persistence of the war in Ukraine, among other factors, have contributed to the reduction in global economic growth forecasts. In the United States, inflation turned out to be lower than estimated and the members of the Federal Open Market Committee (FOMC) reduced the growth forecast for 2023. Nevertheless, the actual level of inflation in that country, its forecasts, and expectations exceed the target. Also, the labor market remains tight, and fiscal policy is still expansionary. In this environment, the Fed raised the expected path for policy interest rates and, with this, the market average estimates higher levels for 2023 than those forecast in October. In the region's emerging economies, country risk premia declined during the quarter and the currencies of those countries appreciated against the US dollar. Considering all the above, for the current year, the Central Bank's technical staff increased the path estimated for the Fed's interest rate, reduced the forecast for growth in the country's external demand, lowered the expected path of oil prices, and kept the country’s risk premium assumption high, but at somewhat lower levels than those anticipated in the previous Monetary Policy Report. Moreover, accumulated inflationary pressures originating from the behavior of the exchange rate would continue to be important. External financial conditions facing the economy have improved recently and could be associated with a more favorable international context for the Colombian economy. So far this year, there has been a reduction in long-term bond interest rates in the markets of developed countries and an increase in the prices of risky assets, such as stocks. This would be associated with a faster-than-expected reduction in inflation in the United States and Europe, which would allow for a less restrictive course for monetary policy in those regions. In this context, the risks of a global recession have been reduced and the global appetite for risk has increased. Consequently, the risk premium continues to decline, the Colombian peso has appreciated significantly, and TES interest rates have decreased. Should this trend consolidate, exchange rate inflationary pressures could be less than what was incorporated into the macroeconomic forecast. Uncertainty about external forecasts and their impact on the country remains high, given the unpredictable course of the war in Ukraine, geopolitical tensions, local uncertainty, and the extensive financing needs of the Colombian government and the economy. High inflation with forecasts and expectations above 3.0%, coupled with surplus demand and a tight labor market are compatible with a contractionary stance on monetary policy that is conducive to the macroeconomic adjustment needed to mitigate the risk of de-anchoring inflation expectations and to ensure that inflation converges to the target. Compared to the forecasts in the October edition of the Monetary Policy Report, domestic demand has been more dynamic, with a higher observed level of output exceeding the productive capacity of the economy. In this context of surplus demand, headline and core inflation continued to trend upward and posted surprising increases. Observed and expected international interest rates increased, the country’s risk premia lessened (but remains at high levels), and accumulated exchange rate pressures are still significant. The technical staff's inflation forecast for 2023 increased and inflation expectations remain well above 3.0%. All in all, the risk of inflation expectations becoming unanchored persists, which would accentuate the generalized indexation process and push inflation even further away from the target. This macroeconomic context requires consolidating a contractionary monetary policy stance that aims to meet the inflation target within the forecast horizon and bring the economy's output to levels closer to its potential. 1.2 Monetary Policy Decision At its meetings in December 2022 and January 2023, Banco de la República’s Board of Directors (BDBR) agreed to continue the process of normalizing monetary policy. In December, the BDBR decided by a majority vote to increase the monetary policy interest rate by 100 basis points (bps) and in its January meeting by 75 bps, bringing it to 12.75% (Graph 1.5). 1/ Seasonally and calendar adjusted. 2/ In the current account aggregate, the pressures for a higher external deficit come from those companies with FDI that are focused on the domestic market. In contrast, profits in the mining and energy sectors are more than offset by the external revenue they generate through exports. Box 1 - Electricity Rates: Recent Developments and Indexation. Author: Édgar Caicedo García, Pablo Montealegre Moreno and Álex Fernando Pérez Libreros Box 2 - Indicators of Household Indebtedness. Author: Camilo Gómez y Juan Sebastián Mariño