Call: +34 974 292 649
Email: joanjoma@unizar.es
Address: Escuela Politécnica Superior Crta de Cuarte, s/n. E-22071 Huesca – Spain
ABOUT ME
Research Interests
My research interests lie primarily in producing biomass-derived carbon materials through thermochemical conversion processes. These renewable-based carbons, which can replace the currently dominant fossil fuel-intensive materials, and then drive innovative and sustainable technologies with circular economy practices.
I began my research career by working on thermochemical conversion of biomass, with a special focus on the behaviour and kinetics of biomass pyrolysis and gasification. In the last years, however, I directed my research activity towards the production of biomass-derived chars for biochar (i.e., char added to soil) and other value-added applications. Since the economic feasibility of large-scale biochar production systems is still unclear (the potential agronomic and environmental benefits of biochar in terms of profit are difficult to quantify), developing biochar-derived engineered carbons for alternative uses other than soil amendment can significantly increase the value chain of the whole system, as well as generate new technologies for biomass upcycling. Among the potential uses of biochar-derived carbons, I particularly centred my attention on three research topics: adsorption in gas phase (e.g., CO2 adsorption in postcombustion conditions), heterogeneous catalysis (e.g., ex situ pyrolysis vapours upgrading), and carbon-based electrodes for energy storage applications (e.g., post-lithium Na- and K-ion batteries).
PUBLICATIONS
2024
Alvira, Darío; Antorán, Daniel; Darjazi, Hamideh; Elia, Giuseppe Antonio; Sebastian, Victor; Manyà, Joan Josep
Sustainable conversion of vine shoots and pig manure into high-performance anode materials for sodium-ion batteries Journal Article
In: Journal of Power Sources, vol. 614, pp. 235043, 2024, ISSN: 0378-7753.
@article{alvira_sustainable_2024,
title = {Sustainable conversion of vine shoots and pig manure into high-performance anode materials for sodium-ion batteries},
author = {Darío Alvira and Daniel Antorán and Hamideh Darjazi and Giuseppe Antonio Elia and Victor Sebastian and Joan Josep Manyà},
url = {https://www.sciencedirect.com/science/article/pii/S0378775324009959},
doi = {10.1016/j.jpowsour.2024.235043},
issn = {0378-7753},
year = {2024},
date = {2024-09-01},
urldate = {2024-09-01},
journal = {Journal of Power Sources},
volume = {614},
pages = {235043},
abstract = {Sodium-ion batteries (SIBs) are considered promising candidates for future grid energy storage, with hard carbons emerging as key commercial anode materials. This study presents a novel approach to synthesize N-doped hard carbons via co-hydrothermal treatment of vine shoots and pig manure and subsequent thermal annealing of the resulting hydrochar. This method enhances the development of micro- and ultra-microporosity in the synthesized hard carbons, with nitrogen, and to a lesser extent phosphorus and sulfur, introduced as doping elements. Furthermore, the incorporation of hydrochloric acid during the hydrothermal step promotes biomass hydrolysis, leading to increased mesoporosity and the formation of microsphere clusters. In the realm of electrochemical performance, an investigation into various ester- and ether-based electrolytes has revealed NaPF6 in diglyme as the best formulation, thanks to its thinner and more stable solid electrolyte interface (SEI). Using this electrolyte, the best-performing electrode showed an initial Coulombic efficiency (ICE) of 73 %, with reversible capacities of 239, 180, 86, and 57 mAh g−1 at 0.1, 1, 5, and 10 A g−1, respectively. In addition, the electrode exhibited a remarkable capacity retention of 88 % after 250 cycles as well as a compatible behavior when paired with a NVPF-based cathode.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Sodium-ion batteries (SIBs) are considered promising candidates for future grid energy storage, with hard carbons emerging as key commercial anode materials. This study presents a novel approach to synthesize N-doped hard carbons via co-hydrothermal treatment of vine shoots and pig manure and subsequent thermal annealing of the resulting hydrochar. This method enhances the development of micro- and ultra-microporosity in the synthesized hard carbons, with nitrogen, and to a lesser extent phosphorus and sulfur, introduced as doping elements. Furthermore, the incorporation of hydrochloric acid during the hydrothermal step promotes biomass hydrolysis, leading to increased mesoporosity and the formation of microsphere clusters. In the realm of electrochemical performance, an investigation into various ester- and ether-based electrolytes has revealed NaPF6 in diglyme as the best formulation, thanks to its thinner and more stable solid electrolyte interface (SEI). Using this electrolyte, the best-performing electrode showed an initial Coulombic efficiency (ICE) of 73 %, with reversible capacities of 239, 180, 86, and 57 mAh g−1 at 0.1, 1, 5, and 10 A g−1, respectively. In addition, the electrode exhibited a remarkable capacity retention of 88 % after 250 cycles as well as a compatible behavior when paired with a NVPF-based cathode.
Antorán, Daniel; Alvira, Darío; Sebastián, Víctor; Manyà, Joan Josep
Enhancing waste hemp hurd-derived anodes for sodium-ion batteries through hydrochloric acid-mediated hydrothermal pretreatment Journal Article
In: Biomass and Bioenergy, vol. 184, pp. 107197, 2024, ISSN: 0961-9534.
@article{antoran_enhancing_2024,
title = {Enhancing waste hemp hurd-derived anodes for sodium-ion batteries through hydrochloric acid-mediated hydrothermal pretreatment},
author = {Daniel Antorán and Darío Alvira and Víctor Sebastián and Joan Josep Manyà},
url = {https://www.sciencedirect.com/science/article/pii/S0961953424001508},
doi = {10.1016/j.biombioe.2024.107197},
issn = {0961-9534},
year = {2024},
date = {2024-05-01},
urldate = {2024-05-01},
journal = {Biomass and Bioenergy},
volume = {184},
pages = {107197},
abstract = {Waste hemp hurd (WHH) was used as a sustainable feedstock for producing hard carbon-based anodes for sodium-ion batteries (SIBs). Two easily scalable production pathways were tested and compared: (1) pyrolysis (at 500 °C) and subsequent annealing at 800, 1000 or 1200 °C, and (2) hydrothermal pretreatment (at 180 °C) and subsequent annealing at the above-mentioned highest temperatures. Results indicated that when a HCl (2 mol m−3) aqueous solution was used as hydrothermal medium, the textural, structural and surface chemistry features linked to the electrochemical performance of the resulting hard carbons improved. The WHH-derived electrode produced via HCl-mediated hydrothermal pretreatment and subsequent annealing at 1000 °C showed an exceptional electrochemical performance in terms of specific capacity (535 mA h g−1 at 30 mA g−1) and rate capability (372, 156, 115, and 83 mA h g−1 at 0.1, 0.5, 1, and 2 A g−1, respectively) when an ester-based electrolyte was used (NaTFSI in EC/DMC). Using an ether-based electrolyte (NaPF6 in diglyme) improved both the ICE (from 69% to 78%) and cycling stability (85% of capacity retention after 300 cycles at 1 A g−1; 91% when current rate returned to 0.1 A g−1). In summary, relatively low-cost WHH-derived carbons are able to deliver an exceptional performance, much better than that reported so far for other biomass-derived carbons, and even close to that exhibited by more expensive and complex composite and hybrid materials.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Waste hemp hurd (WHH) was used as a sustainable feedstock for producing hard carbon-based anodes for sodium-ion batteries (SIBs). Two easily scalable production pathways were tested and compared: (1) pyrolysis (at 500 °C) and subsequent annealing at 800, 1000 or 1200 °C, and (2) hydrothermal pretreatment (at 180 °C) and subsequent annealing at the above-mentioned highest temperatures. Results indicated that when a HCl (2 mol m−3) aqueous solution was used as hydrothermal medium, the textural, structural and surface chemistry features linked to the electrochemical performance of the resulting hard carbons improved. The WHH-derived electrode produced via HCl-mediated hydrothermal pretreatment and subsequent annealing at 1000 °C showed an exceptional electrochemical performance in terms of specific capacity (535 mA h g−1 at 30 mA g−1) and rate capability (372, 156, 115, and 83 mA h g−1 at 0.1, 0.5, 1, and 2 A g−1, respectively) when an ester-based electrolyte was used (NaTFSI in EC/DMC). Using an ether-based electrolyte (NaPF6 in diglyme) improved both the ICE (from 69% to 78%) and cycling stability (85% of capacity retention after 300 cycles at 1 A g−1; 91% when current rate returned to 0.1 A g−1). In summary, relatively low-cost WHH-derived carbons are able to deliver an exceptional performance, much better than that reported so far for other biomass-derived carbons, and even close to that exhibited by more expensive and complex composite and hybrid materials.
Maziarka, Przemyslaw; Kienzl, Norbert; Dieguez-Alonso, Alba; Fierro, Vanessa; Celzard, Alain; Arauzo, Pablo J.; Hedin, Niklas; Prins, Wolter; Anca-Couce, Andrés; Manyà, Joan Josep; Ronsse, Frederik
In: Energy & Fuels, 2024, ISSN: 0887-0624, (Publisher: American Chemical Society).
@article{maziarka_part_2024,
title = {Part 1─Impact of Pyrolysis Temperature and Wood Particle Length on Vapor Cracking and Char Porous Texture in Relation to the Tailoring of Char Properties},
author = {Przemyslaw Maziarka and Norbert Kienzl and Alba Dieguez-Alonso and Vanessa Fierro and Alain Celzard and Pablo J. Arauzo and Niklas Hedin and Wolter Prins and Andrés Anca-Couce and Joan Josep Manyà and Frederik Ronsse},
url = {https://doi.org/10.1021/acs.energyfuels.4c00937},
doi = {10.1021/acs.energyfuels.4c00937},
issn = {0887-0624},
year = {2024},
date = {2024-05-01},
urldate = {2024-05-01},
journal = {Energy & Fuels},
abstract = {Pore size distribution is a key parameter in the performance of biobased pyrolytic char in novel applications. In industrial-scale production, the size of feedstock particles typically exceeds a few millimeters. For such particle sizes, it is a challenge to tailor the final properties of the char based only on the process conditions (experimental and modeling-wise). Pyrolysis studies of single particles larger than a few millimeters provide data sets useful for modeling and optimization of the process. Part 1 of this research focused on the pyrolysis of single particles of beech wood, secondary cracking, and its effect on the char porous texture. It contains a quantitative assessment of the effects of five conversion temperatures (from 300 to 840 °C) and two particle dimensions (Ø8 × 10 mm and Ø8 × 16 mm) on the composition of the pyrolysis vapors and pore morphology of the char. Results from real-time temperature and mass changes are presented along with release profiles of 15 vapor constituents measured by infrared spectroscopy. Furthermore, characterization of the collected bio-oil (using GC-MS/FID) and the textural hierarchical structured char (through N2 and CO2 adsorption, Hg porosimetry, and scanning electron microscopy (SEM)) was performed. Cracking of vapors above 500 °C was compound-specific. The polyaromatic hydrocarbons (PAHs) yield, between 680 and 840 °C, increased 5 times for 10 mm particles and 9 times for 16 mm ones. Besides temperature, PAH yield was suspected to correlate with particle length and PAHs/soot deposition in the micropores. Results showed that the macropores accounted for over 80% of the total pore volume, regardless of the temperature and particle length. Increasing the particle length by 60% caused a reduction in the specific surface area (ca. 15% at 840 °C) of the resulting char, mainly due to a reduction in microporosity. Based on the findings, the production conditions for a specific char application are suggested. The obtained data will be used in Part 2 of this research, devoted to subsequent CFD modeling of the process.},
note = {Publisher: American Chemical Society},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Pore size distribution is a key parameter in the performance of biobased pyrolytic char in novel applications. In industrial-scale production, the size of feedstock particles typically exceeds a few millimeters. For such particle sizes, it is a challenge to tailor the final properties of the char based only on the process conditions (experimental and modeling-wise). Pyrolysis studies of single particles larger than a few millimeters provide data sets useful for modeling and optimization of the process. Part 1 of this research focused on the pyrolysis of single particles of beech wood, secondary cracking, and its effect on the char porous texture. It contains a quantitative assessment of the effects of five conversion temperatures (from 300 to 840 °C) and two particle dimensions (Ø8 × 10 mm and Ø8 × 16 mm) on the composition of the pyrolysis vapors and pore morphology of the char. Results from real-time temperature and mass changes are presented along with release profiles of 15 vapor constituents measured by infrared spectroscopy. Furthermore, characterization of the collected bio-oil (using GC-MS/FID) and the textural hierarchical structured char (through N2 and CO2 adsorption, Hg porosimetry, and scanning electron microscopy (SEM)) was performed. Cracking of vapors above 500 °C was compound-specific. The polyaromatic hydrocarbons (PAHs) yield, between 680 and 840 °C, increased 5 times for 10 mm particles and 9 times for 16 mm ones. Besides temperature, PAH yield was suspected to correlate with particle length and PAHs/soot deposition in the micropores. Results showed that the macropores accounted for over 80% of the total pore volume, regardless of the temperature and particle length. Increasing the particle length by 60% caused a reduction in the specific surface area (ca. 15% at 840 °C) of the resulting char, mainly due to a reduction in microporosity. Based on the findings, the production conditions for a specific char application are suggested. The obtained data will be used in Part 2 of this research, devoted to subsequent CFD modeling of the process.
Maziarka, Przemyslaw; Kienzl, Norbert; Dieguez-Alonso, Alba; Prins, Wolter; Arauzo, Pablo J.; Skreiberg, Øyvind; Anca-Couce, Andrés; Manyà, Joan Josep; Ronsse, Frederik
In: Energy & Fuels, 2024, ISSN: 0887-0624, (Publisher: American Chemical Society).
@article{maziarka_part_2024-1,
title = {Part 2─Tailoring of Pyrolytic Char Properties with a Single Particle CFD Model with a Focus on the Impact of Shrinking, Vapor Cracking, and Char Permeability},
author = {Przemyslaw Maziarka and Norbert Kienzl and Alba Dieguez-Alonso and Wolter Prins and Pablo J. Arauzo and Øyvind Skreiberg and Andrés Anca-Couce and Joan Josep Manyà and Frederik Ronsse},
url = {https://doi.org/10.1021/acs.energyfuels.4c00942},
doi = {10.1021/acs.energyfuels.4c00942},
issn = {0887-0624},
year = {2024},
date = {2024-05-01},
urldate = {2024-05-01},
journal = {Energy & Fuels},
abstract = {The prediction of the structural properties of biobased carbonaceous materials of pyrolytic origin (chars) with only base feedstock properties and process conditions still poses a challenge that hinders char tailoring for novel applications. CFD modeling of single biomass particle conversion can help solve this issue since it allows for the quantification of relations between parameters that are difficult to measure. A model for char tailoring must include a validated representation of the structural changes coupled to all other relevant phenomena occurring during conversion. Part 2 of this study focuses on finding the description of the mentioned aspects to achieve the highest precision of prediction of the structural changes in char by a CFD model. The investigation in Part 2 is composed of three cases focused on accurate description and prediction of (1) bulk density and porosity, (2) secondary vapor reactions on yields and soot formation, and (3) permeability, as well as the outflux and conversion of evolved vapors. The experimental results from Part 1 and the literature data were used to find appropriate descriptions of phenomena and assess the accuracy of the model. The model results indicate that for both particle lengths (10 and 16 mm), a high accuracy of prediction of base structural parameters was achieved. The average prediction error for temperatures between 400 and 840 °C of bulk density was 31 ± 15 kg/m3, and the porosity was 1.8 ± 1.1 vol %. The results also show a low error in the prediction of bulk product yields (dry basis) over the mentioned temperature range, which were: for char 2.8 ± 1.1 wt %, for the condensable fraction 6.5 ± 3.3 wt %, and for the pyrolysis gas 4.1 ± 1.9 wt %. The distribution of secondary char formation was found to be nonuniform below 500 °C. The changes in permeability had a minor influence on the vapor outflux but a non-negligible effect on the soot formation, especially at 840 °C. The results indicate a need for further improvement of the primary degradation model to increase the accuracy of the effect of soot formation on the char structure.},
note = {Publisher: American Chemical Society},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The prediction of the structural properties of biobased carbonaceous materials of pyrolytic origin (chars) with only base feedstock properties and process conditions still poses a challenge that hinders char tailoring for novel applications. CFD modeling of single biomass particle conversion can help solve this issue since it allows for the quantification of relations between parameters that are difficult to measure. A model for char tailoring must include a validated representation of the structural changes coupled to all other relevant phenomena occurring during conversion. Part 2 of this study focuses on finding the description of the mentioned aspects to achieve the highest precision of prediction of the structural changes in char by a CFD model. The investigation in Part 2 is composed of three cases focused on accurate description and prediction of (1) bulk density and porosity, (2) secondary vapor reactions on yields and soot formation, and (3) permeability, as well as the outflux and conversion of evolved vapors. The experimental results from Part 1 and the literature data were used to find appropriate descriptions of phenomena and assess the accuracy of the model. The model results indicate that for both particle lengths (10 and 16 mm), a high accuracy of prediction of base structural parameters was achieved. The average prediction error for temperatures between 400 and 840 °C of bulk density was 31 ± 15 kg/m3, and the porosity was 1.8 ± 1.1 vol %. The results also show a low error in the prediction of bulk product yields (dry basis) over the mentioned temperature range, which were: for char 2.8 ± 1.1 wt %, for the condensable fraction 6.5 ± 3.3 wt %, and for the pyrolysis gas 4.1 ± 1.9 wt %. The distribution of secondary char formation was found to be nonuniform below 500 °C. The changes in permeability had a minor influence on the vapor outflux but a non-negligible effect on the soot formation, especially at 840 °C. The results indicate a need for further improvement of the primary degradation model to increase the accuracy of the effect of soot formation on the char structure.
2023
Alvira, Darío; Antorán, Daniel; Vidal, Mariano; Sebastián, Víctor; Manyà, Joan Josep
Vine Shoots-Derived Hard Carbons as Anodes for Sodium-Ion Batteries: Role of Annealing Temperature in Regulating Their Structure and Morphology Journal Article
In: Batteries & Supercaps, vol. n/a, no. n/a, pp. e202300233, 2023, ISSN: 2566-6223, (_eprint: https://onlinelibrary.wiley.com/doi/pdf/10.1002/batt.202300233).
@article{alvira_vine_nodate,
title = {Vine Shoots-Derived Hard Carbons as Anodes for Sodium-Ion Batteries: Role of Annealing Temperature in Regulating Their Structure and Morphology},
author = {Darío Alvira and Daniel Antorán and Mariano Vidal and Víctor Sebastián and Joan Josep Manyà},
url = {https://onlinelibrary.wiley.com/doi/abs/10.1002/batt.202300233},
doi = {10.1002/batt.202300233},
issn = {2566-6223},
year = {2023},
date = {2023-08-02},
urldate = {2023-08-02},
journal = {Batteries & Supercaps},
volume = {n/a},
number = {n/a},
pages = {e202300233},
abstract = {Sodium-ion batteries (SIBs) are considered one of the most promising large-scale and low-cost energy storage systems due to the abundance and low price of sodium. Herein, hard carbons from a sustainable biomass feedstock (vine shoots) were synthesized via a simple two-step carbonization process at different highest temperatures to be used as anodes in SIBs. The hard carbon produced at 1200 °C delivered the highest reversible capacity (270 mAh g−1 at 0.03 A g−1, with an acceptable initial coulombic efficiency of 71 %) since a suitable balance between the pseudographitic domains growth and the retention of microporosity, defects, and functional groups was achieved. A prominent cycling stability with a capacity retention of 97 % over 315 cycles was also attained. Comprehensive characterization unraveled a three-stage sodium storage mechanism based on adsorption, intercalation, and filling of pores. A remarkable specific capacity underestimation of up to 38 % was also found when a two-electrode half-cell configuration was employed to measure the rate performance. To avoid this systematic error caused by the counter/reference electrode polarization, we strongly recommend the use of a three-electrode setup or a full-cell configuration to correctly evaluate the anode response at moderate and high current rates.},
note = {_eprint: https://onlinelibrary.wiley.com/doi/pdf/10.1002/batt.202300233},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
Sodium-ion batteries (SIBs) are considered one of the most promising large-scale and low-cost energy storage systems due to the abundance and low price of sodium. Herein, hard carbons from a sustainable biomass feedstock (vine shoots) were synthesized via a simple two-step carbonization process at different highest temperatures to be used as anodes in SIBs. The hard carbon produced at 1200 °C delivered the highest reversible capacity (270 mAh g−1 at 0.03 A g−1, with an acceptable initial coulombic efficiency of 71 %) since a suitable balance between the pseudographitic domains growth and the retention of microporosity, defects, and functional groups was achieved. A prominent cycling stability with a capacity retention of 97 % over 315 cycles was also attained. Comprehensive characterization unraveled a three-stage sodium storage mechanism based on adsorption, intercalation, and filling of pores. A remarkable specific capacity underestimation of up to 38 % was also found when a two-electrode half-cell configuration was employed to measure the rate performance. To avoid this systematic error caused by the counter/reference electrode polarization, we strongly recommend the use of a three-electrode setup or a full-cell configuration to correctly evaluate the anode response at moderate and high current rates.