Controlled nanoscale deposition of discharge products in Na-O2 batteries by inducing nucleation on edge-defected graphene cathode

Marina Enterría^a, Lidia Medinilla^a, Shaikh Nayeem Faisal^b, Yan Zhang^a, Juan Miguel López del Amo^a, Idoia Ruiz de Larramendi^c, Luis Lezama^c, David Officer^b, Nagore Ortiz Vitoriano^a^,^d

^aCenter for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, 01510.

^bInstitute for Superconducting and Electronic Materials, Australian Institute for Innovative Materials (AIIM) Facility, University of Wollongong, Innovation Campus, North Wollongong, NSW 2500, Australia

^cDepartment of Organic and Inorganic Chemistry, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, 48940 Leioa, Spain

^dIkerbasque, Basque Foundations for Science, María Díaz de Haro 3, 48013 Bilbao, Spain.

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Spring 2024 Conference (MATSUS24)

#GENBAT - Next-generation battery technologies towards sustainability

Barcelona, Spain, 2024 March 4th - 8th

Organizers: REBECA MARCILLA, Cristina Pozo-Gonzalo and Magda Titirici

Oral, Marina Enterría, presentation 343
DOI: https://doi.org/10.29363/nanoge.matsus.2024.343
Publication date: 18th December 2023

Lithium–ion batteries (LiBs) are currently leading the portable electronic market due to their great cyclability. However, the current energy demand is pushing the limits of LiBs in terms of energy density (100 – 265 Wh kg⁻¹), cycle life (1000 cycles at > 80% of capacity) and charge/discharge rate capabilities (1C). Aprotic sodium-oxygen batteries (Na-O₂) are promising devices to tackle such energy demands due to their much higher theoretical energy density (1086 Wh kg^-1 based on sodium superoxide discharge product, NaO₂). These conversion batteries reduce oxygen gas to form solid NaO₂, which is deposited on the surface of the cathode during discharge. Rechargeability depends on an efficient charge, where complete redissolution of the superoxide in the organic electrolyte is required to further release all the oxygen back. The size, the distribution, the morphology and the chemical nature of the solid deposits are crucial parameters for the battery performance, due to the electronically insulating nature of NaO₂. Thus, the passivation of the cathode surface by NaO₂ generally leads to a premature death of the battery. Electrolyte formulation has demonstrated to have a profound effect on the morphology of the NaO₂ cubes by affecting their solvation and crystallization processes [1,2]. It is believed that small micrometric particles form a film and promote passivation while large cubes enhance the electron conduction towards the discharge product. However, recent works have demonstrated the importance of the cathode surface chemistry on the nucleation and growth of the discharge products [3-5]. A controlled surface-mediated mechanism enabling the deposition of defined and homogeneously distributed nanometric particles is, in fact, beneficial for battery performance as; i) the discharge product will not insulate the cathode surface by an effective utilization of its surface area and ii) the oxidation of nanosized NaO₂ during charge will be facilitated by nanometric particles at a still conductive electrode.

In this work, edge-defected graphene nanoplatelets will be discussed as cathode in Na-O₂ batteries which act as nucleation points, promoting homogeneous nucleation of nanosized and well-defined NaO₂ cubes at the surface of the conductive graphene air-cathode.

References:

[1] Ortiz-Vitoriano, N.; Monterrubio, I., Garcia-Quintana, L.; López Del Amo, J.M.; Chen, F.; T. Rojo, T.; Howlett, P. C.; Forsyth, M.; Pozo-Gonzalo, C. Highly Homogeneous Sodium Superoxide Growth in Na-O2 Batteries Enabled by a Hybrid Electrolyte. ACS Energy. Lett. 2020, 5, 903–909.

[2] Xia, C.; Black,R; Fernandes, R.; Adams, A., Nazar, L.F. The critical role of phase-transfer catalysis in aprotic sodium oxygen batteries. Nature Chemistry, 2015, 7, 496–501.

[3] Lutz, L.; Alves Dalla Corte, D.; Chen, Y.; Batuk, D.; Johnson, L. R.; Abakumov, A.; Yate, L.; Azaceta, E.; Bruce, P. G.; Tarascon, J.M.; Grimaud, A. The Role of the Electrode Surface in Na–Air Batteries: Insights in Electrochemical Product Formation and Chemical Growth of NaO2. Adv Energy Mater, 2018, 8, 1701581.

[4] Enterría, M.; Gómez-Urbano, J.L., Munuera, J.M.; Villar-Rodil, S.; Carriazo, D.; Paredes, J.I.; Ortiz-Vitoriano, N. Boosting the Performance of Graphene Cathodes in Na–O2 Batteries by Exploiting the Multifunctional Character of Small Biomolecules. Small, 2021, 17, 2005034.

[5] Enterría, M.; Botas, C.; Gómez-Urbano, J.L., Acebedo, B.; López Del Amo, J. M.; Carriazo, D.; Rojo, T. N. Ortiz-Vitoriano, N. Pathways towards high performance Na–O2 batteries: tailoring graphene aerogel cathode porosity & nanostructure. J. Mater Chem A Mater, 2018, 6, 20778–20787

Acknowledgements:

This work was funded by the European Union (Graphene Flagship-Core 3, Grant number 881603), by grant PID2019-107468RB-C21 funded by MCIN/AEI/10.13039/501100011033 and Gobierno Vasco/Eusko Jaurlaritza (project IT1546-22). N. Ortiz-Vitoriano thanks the Grant RYC2020-030104-I funded by MCIN/AEI/ 10.13039/501100011033 and by “ESF Investing in your future”.

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