Monoclinic and Orthorhombic NaMnO 2 for Secondary Batteries: A Comparative Study

Jessica Manzi, Annalisa Paolone, Oriele Palumbo, Domenico Corona, Arianna Massaro, Rossana Cavaliere, Ana Belén Muñoz-García, Francesco Trequattrini, Michele Pavone and Sergio Brutti
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Jessica Manzi: Dipartimento di Scienze, Università della Basilicata, Viale dell’Ateneo Lucano 10, 85100 Potenza, Italy
Annalisa Paolone: Istituto dei Sistemi Complessi (ICS-CNR), Via dei Taurini, 00185 Roma, Italy
Oriele Palumbo: Istituto dei Sistemi Complessi (ICS-CNR), Via dei Taurini, 00185 Roma, Italy
Domenico Corona: Dipartimento di Chimica, Università di Roma La Sapienza, Piazzale Aldo Moro 5, 00185 Roma, Italy
Arianna Massaro: Dipartimento di Scienze Chimiche, Università degli Studi di Napoli “Federico II”, Via Cintia 21, 80126 Napoli, Italy
Rossana Cavaliere: Dipartimento di Scienze Chimiche, Università degli Studi di Napoli “Federico II”, Via Cintia 21, 80126 Napoli, Italy
Ana Belén Muñoz-García: Dipartimento di Fisica “E. Pancini”, Università degli Studi di Napoli “Federico II”, Via Cintia 21, 80126 Napoli, Italy
Francesco Trequattrini: Dipartimento di Fisica, Università di Roma La Sapienza, Piazzale Aldo Moro 5, 00185 Roma, Italy
Michele Pavone: Dipartimento di Scienze Chimiche, Università degli Studi di Napoli “Federico II”, Via Cintia 21, 80126 Napoli, Italy
Sergio Brutti: Istituto dei Sistemi Complessi (ICS-CNR), Via dei Taurini, 00185 Roma, Italy

Energies, 2021, vol. 14, issue 5, 1-13

Abstract: In this manuscript, we report a detailed physico-chemical comparison between the α- and β-polymorphs of the NaMnO 2 compound, a promising material for application in positive electrodes for secondary aprotic sodium batteries. In particular, the structure and vibrational properties, as well as electrochemical performance in sodium batteries, are compared to highlight differences and similarities. We exploit both laboratory techniques (Raman spectroscopy, electrochemical methods) and synchrotron radiation experiments (Fast-Fourier Transform Infrared spectroscopy, and X-ray diffraction). Notably the vibrational spectra of these phases are here reported for the first time in the literature as well as the detailed structural analysis from diffraction data. DFT+U calculations predict both phases to have similar electronic features, with structural parameters consistent with the experimental counterparts. The experimental evidence of antisite defects in the beta-phase between sodium and manganese ions is noticeable. Both polymorphs have been also tested in aprotic batteries by comparing the impact of different liquid electrolytes on the ability to de-intercalated/intercalate sodium ions. Overall, the monoclinic α-NaMnO 2 shows larger reversible capacity exceeding 175 mAhg −1 at 10 mAg −1 .

Keywords: NaMnO 2; polymorphs; X-ray diffraction; vibrational spectroscopy; sodium batteries (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2021
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