Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

Dey, Sunita; Zeng, Dongli; Adamson, Paul; Cabana, Jordi; Indris, Sylvio; Lu, Jingyu; Clarke, Simon J.; Grey, Clare P.

doi:10.1021/acs.chemmater.1c00375

Title: Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

Journal Article · Mon May 24 00:00:00 EDT 2021 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.1c00375· OSTI ID:1816689

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Univ. of Cambridge (United Kingdom). Dept. of Chemistry
State Univ. of New York (SUNY), Stony Brook, NY (United States). Dept. of Chemistry
Univ. of Oxford (United Kingdom). Inorganic Chemistry Lab. Dept. of Chemistry
Univ. of Oxford (United Kingdom). Inorganic Chemistry Lab. Dept. of Chemistry
Univ. of Oxford (United Kingdom). Inorganic Chemistry Lab. Dept. of Chemistry; State Univ. of New York (SUNY), Stony Brook, NY (United States). Dept. of Chemistry

The electrochemical lithiation and delithiation of the layered oxysulfide Sr₂MnO₂Cu_4-δS₃ has been investigated by using a combination of in situ powder X-ray diffraction and ex situ neutron powder diffraction, X-ray absorption and ⁷Li NMR spectroscopy, together with a range of electrochemical experiments. Sr₂MnO₂Cu_4-δS₃ consists of [Sr₂MnO₂] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu_4-δS₃] (δ ≈ 0.5) anionic layers. It undergoes a combined displacement/intercalation (CDI) mechanism on reaction with Li, where the inserted Li replaces Cu, forming Li₄S₃ slabs and Cu⁺ is reduced and extruded as metallic particles. For the initial 2-3% of the first discharge process, the vacant sites in the sulfide layer are filled by Li; Cu extrusion then accompanies further insertion of Li. Mn^2.5+ is reduced to Mn²⁺ during the first half of the discharge. The overall charging process involves the removal of Li and re-insertion of Cu into the sulfide layers with re-oxidation of Mn²⁺ to Mn^2.5+. However, due to the different diffusivities of Li and Cu, the processes operating on charge are quite different from those operating during the first discharge: charging to 2.75 V results in the removal of most of the Li, little reinsertion of Cu, and good capacity retention. A charge to 3.75 V is required to fully reinsert Cu, which results in significant changes to the sulfide sublattice during the following discharge and poor capacity retention. This detailed structure-property investigation will promote the design of new functional electrodes with improved device performance.

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Research Organization:: State Univ. of New York (SUNY), Stony Brook, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0001294

OSTI ID:: 1816689

Journal Information:: Chemistry of Materials, Vol. 33, Issue 11; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
X-ray absorption near edge spectroscopy
Sulfides
Layers
Diffraction
Transition metals

Title: Structural Evolution of Layered Manganese Oxysulfides during Reversible Electrochemical Lithium Insertion and Copper Extrusion

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