Superior Lithium Storage Capacity of α‐MnS Nanoparticles Embedded in S‐Doped Carbonaceous Mesoporous Frameworks. Issue 43 (1st October 2019)

• Record Type: Journal Article
• Authors: Ma, Yuan; Ma, Yanjiao; Kim, Guk‐Tae; Diemant, Thomas; Behm, Rolf Jürgen; Geiger, Dorin; Kaiser, Ute; Varzi, Alberto; Passerini, Stefano
• Is Part Of: Advanced energy materials. Volume 9:Issue 43(2019)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2019-10-01
• Subjects: α‐MnS nanoparticles -- in situ dilatometry -- in situ XRD/reaction mechanism -- lithium‐ion batteries -- S‐doped carbonaceous frameworks; Energy harvesting -- Materials -- Periodicals; Energy conversion -- Materials -- Periodicals; Energy storage -- Materials -- Periodicals; Photovoltaics -- Periodicals; Fuel cells -- Periodicals; Thermoelectric materials -- Periodicals; 621.31
• DOI: 10.1002/aenm.201902077
• Languages: English
• ISSNs: 1614-6832

Abstract

Abstract: Herein, a Mn‐based metal–organic framework is used as a precursor to obtain well‐defined α‐MnS/S‐doped C microrod composites. Ultrasmall α‐MnS nanoparticles (3–5 nm) uniformly embedded in S‐doped carbonaceous mesoporous frameworks (α‐MnS/SCMFs) are obtained in a simple sulfidation reaction. As‐obtained α‐MnS/SCMFs shows outstanding lithium storage performance, with a specific capacity of 1383 mAh g −1 in the 300th cycle or 1500 mAh g −1 in the 120th cycle (at 200 mA g −1 ) using copper or nickel foil as the current collector, respectively. The significant (pseudo)capacitive contribution and the stable composite structure of the electrodes result in impressive rate capabilities and outstanding long‐term cycling stability. Importantly, in situ X‐ray diffraction measurements studies on electrodes employing various metal foils/disks as current collector reveal the occurrence of the conversion reaction of CuS at (de)lithiation process when using copper foil as the current collector. This constitutes the first report of the reaction mechanism for α‐MnS, eventually forming metallic Mn and Li2 S. In situ dilatometry measurements demonstrate that the peculiar structure of α‐MnS/SCMFs effectively restrains the electrode volume variation upon repeated (dis)charge processes. Finally, α‐MnS/SCMFs electrodes present an impressive performance when coupled in a full cell with commercial LiMn1/3 Co1/3 Ni1/3 O2 cathodes. Abstract : The composite of α‐MnS and S‐doped carbon derived from Mn‐based metal organic frameworks enables outstanding lithium storage performance in half/full Li‐ion cells, benefiting from its structural and compositional features. The study of the lithium storage mechanism reveals that alongside the conversion reaction of α‐MnS, CuS, which is formed during the electrode coating on Cu foil, is also undergoing the conversion process.