ACS Applied Energy Materials, volume 1, issue 11, pages 5842-5846

Enhancing Na+ Extraction Limit through High Voltage Activation of the NASICON-Type Na4MnV(PO4)3 Cathode

Maxim V. Zakharkin ^{1, 2}

Oleg A. Drozhzhin ^{1, 2}

Ivan V. Tereshchenko ^{1, 2}

D. O. Chernyshov ^{3, 4}

Dmitry Chernyshov ^{3, 4}

Artem M. Abakumov ¹

Evgeny V. Antipov ^{1, 2}

Keith J Stevenson ¹

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Skolkovo Institute of Science and Technology, 3 Nobel Street, Moscow 143025, Russia |

Lomonosov Moscow State University, 1/3 Leninskie gory, Moscow 119991, Russia |

Swiss−Norwegian Beamlines, European Synchrotron, 71 Rue des Martyrs, Grenoble 38043, France |

⁴

Peter the Great St. Petersburg Polytechnic University, 29 Polytekhnicheskaya Street, Saint-Petersburg 195251, Russia |

Publication type: Journal Article

Publication date: 2018-11-02

American Chemical Society (ACS)

Journal: ACS Applied Energy Materials

scimago Q1

SJR: 1.467

CiteScore: 10.3

Impact factor: 5.4

ISSN: 25740962

DOI: 10.1021/acsaem.8b01269

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Materials Chemistry

Electrochemistry

Electrical and Electronic Engineering

Energy Engineering and Power Technology

Chemical Engineering (miscellaneous)

Abstract

Sodium (de)intercalation in the Na4MnV(PO4)3 NASICON-type cathode has been studied with operando synchrotron X-ray powder diffraction and galvanostatic cycling up to 3.8 and 4.0 V cutoff voltages. Symmetry reduction from rhombohedral to monoclinic was observed immediately after the start of the electrochemical desodiation, with restoring of the rhombohedral phase at 3.8 V. Cycling within the 2.5–3.8 V potential range proceeds through both solid-solution and two-phase processes. An additional voltage plateau at ∼3.9 V is observed, associated with “unlocking” of the Na1 site in the rhombohedral phase. Reverse insertion of Na+ cations proceeds via the entire solid-solution region. The experimentally observed discharge capacity increases by ≈14% after raising cutoff voltage.

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