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

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The electrochemical lithiation and delithiation of the layered oxysulfide Sr2MnO2Cu4-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. Sr2MnO2Cu4-δS3 consists of [Sr2MnO2] perovskite-type cationic layers alternating with highly defective antifluorite-type [Cu4-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. Mn2.5+ 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 Mn2.5+. 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.



40 Engineering, 4016 Materials Engineering, 34 Chemical Sciences, 3406 Physical Chemistry

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Chem Mater

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American Chemical Society (ACS)


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Engineering and Physical Sciences Research Council (EP/P003532/1)
Engineering and Physical Sciences Research Council (EP/M009521/1)
We thank the UK EPSRC for a studentship for PA and for funding through grants EP/E025447/1 and EP/P018874/1 and the UK STFC for access to the ISIS facility. We acknowledge DST Overseas Visiting Fellowship in Nano Science and Technology, Government of India (July 2018-June 2019). We acknowledge the funding from EPSRC grants EP/M009521/1 DJR00640 and EP/P003532/1. This work was also supported as part of the Northeastern Center for Chemical Energy Storage (NECCES), an Energy Frontier Re-search Center funded by the U.S. Department of Energy, Office of Science.