Call: +34 974 239 320
Email: dalvira@unizar.es
Address: Escuela Politécnica Superior, Crta de Cuarte, s/n. E-22071 Huesca – Spain
ABOUT ME
Research Interests
- Producing biomass-derived chars by pyrolysis of agricultural wastes.
- Developing advanced carbon materials for thermal, catalytic and electrochemical applications.
- Activation and doping of engineered carbons as anodes for sodium-ion batteries.
Projects
- MEDWASTE —Mediterranean Agricultural Wastes: Environmentally Sustainable Resource for an Innovative Renewable Energy Technology (PCIN-2017-048)
- BIOCARB-ion —Engineered biochar-derived carbons as anodes for sodium- and potassium-ion batteries (PID2019-107737RB-I00)
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.
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.
Antorán, Daniel; Alvira, Darío; Peker, M. Eser; Malón, Hugo; Irusta, Silvia; Sebastián, Víctor; Manyà, Joan Josep
Waste Hemp Hurd as a Sustainable Precursor for Affordable and High-Rate Hard Carbon-Based Anodes in Sodium-Ion Batteries Journal Article
In: Energy Fuels, vol. 37, no. 13, pp. 9650–9661, 2023, ISSN: 0887-0624, (Publisher: American Chemical Society).
@article{antoran_waste_2023,
title = {Waste Hemp Hurd as a Sustainable Precursor for Affordable and High-Rate Hard Carbon-Based Anodes in Sodium-Ion Batteries},
author = {Daniel Antorán and Darío Alvira and M. Eser Peker and Hugo Malón and Silvia Irusta and Víctor Sebastián and Joan Josep Manyà},
url = {https://doi.org/10.1021/acs.energyfuels.3c01040},
doi = {10.1021/acs.energyfuels.3c01040},
issn = {0887-0624},
year = {2023},
date = {2023-07-01},
urldate = {2023-07-01},
journal = {Energy Fuels},
volume = {37},
number = {13},
pages = {9650–9661},
abstract = {The present study reports the promising potential of waste hemp-hurd-derived carbons as anodes in sodium-ion batteries (SIBs). Carbons were produced through an easily scalable process consisting of pyrolysis of raw biomass at 500 °C followed by mild chemical activation of the resulting char through wet impregnation with K2CO3 and subsequent heating of the solid phase (after filtration and drying) up to 700 or 800 °C under nitrogen. The best electrochemical performance was observed for the hard carbon activated at a char-K2CO3 mass ratio of 1:4 and heated up to 800 °C, which exhibited an excellent initial coulombic efficiency (73%) and achieved reversible charge capacities of 267 and 79 mAh g–1 at 0.03 and 1 A g–1, respectively. This material also exhibited an impressive cyclic stability and rate capability, with a capacity retention of 96% after 300 cycles at a current density of 2 A g–1. This more than satisfactory performance could be related to the textural and structural features of the hard carbon, which include moderate interconnected microporosity (with pore sizes below 1 nm), an appropriate concentration of defects in the carbon structure, relatively large interplanar distances, and a certain number of closed pores.},
note = {Publisher: American Chemical Society},
keywords = {},
pubstate = {published},
tppubtype = {article}
}
The present study reports the promising potential of waste hemp-hurd-derived carbons as anodes in sodium-ion batteries (SIBs). Carbons were produced through an easily scalable process consisting of pyrolysis of raw biomass at 500 °C followed by mild chemical activation of the resulting char through wet impregnation with K2CO3 and subsequent heating of the solid phase (after filtration and drying) up to 700 or 800 °C under nitrogen. The best electrochemical performance was observed for the hard carbon activated at a char-K2CO3 mass ratio of 1:4 and heated up to 800 °C, which exhibited an excellent initial coulombic efficiency (73%) and achieved reversible charge capacities of 267 and 79 mAh g–1 at 0.03 and 1 A g–1, respectively. This material also exhibited an impressive cyclic stability and rate capability, with a capacity retention of 96% after 300 cycles at a current density of 2 A g–1. This more than satisfactory performance could be related to the textural and structural features of the hard carbon, which include moderate interconnected microporosity (with pore sizes below 1 nm), an appropriate concentration of defects in the carbon structure, relatively large interplanar distances, and a certain number of closed pores.
2022
Alvira, Darío; Antorán, Daniel; Manyà, Joan Josep
Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guide Journal Article
In: Journal of Energy Chemistry, vol. 75, pp. 457–477, 2022, ISSN: 2095-4956.
@article{Alvira2022b,
title = {Assembly and electrochemical testing of renewable carbon-based anodes in SIBs: A practical guide},
author = {Darío Alvira and Daniel Antorán and Joan Josep Manyà},
url = {https://linkinghub.elsevier.com/retrieve/pii/S209549562200479X},
doi = {10.1016/J.JECHEM.2022.09.002},
issn = {2095-4956},
year = {2022},
date = {2022-12-01},
urldate = {2022-12-01},
journal = {Journal of Energy Chemistry},
volume = {75},
pages = {457--477},
publisher = {Elsevier},
keywords = {},
pubstate = {published},
tppubtype = {article}
}