Nanoscale α-MnS crystallites grown on N-S co-doped rGO as a long-life and high-capacity anode material of Li-ion batteries

Liu, Boli; Liu, Zhengjiao; Li, Dan; Guo, Pengqian; Liu, Dequan; Shang, Xiaonan; Lv, Mingzhi; He, Deyan

doi:10.1016/j.apsusc.2017.04.230

Cited by 70 publications

(34 citation statements)

References 48 publications

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“…[3,4] Taken together, the results indicate that S not only reacts with Mn atoms, but dopes the porous carbonaceous framework too. [3,4,20] Finally, the O 1s spectrum in Figure 1f displays two peaks at binding energies of 531.8 and 533.1 eV, representing the CO and CO groups, respectively, which is in agreement with the C 1s XPS spectrum. [7,9,21,22] It should be mentioned that there is also a small feature at 529.8 eV, suggesting the formation of MnO impurities.…”

Section: Synthesis and Characteristics Of α-Mns/scmfssupporting

confidence: 68%

“…[3,12,[23][24][25] Furthermore, it was reported that the broad feature at 2.70 V in the anodic sweep could be due to the further oxidation of Mn 2+ to obtain MnS 1+z (0<z≤1) . [20] However, as it will be shown later, the real origin of these features is a side reaction involving the Cu current collector. Overall, α-MnS/ SCMFs/Cu exhibited a higher specific current than α-MnS/Cu, which can be explained by a (pseudo)capacitive contribution (to be discussed later in more detail) [26] and additional lithium-ion storage sites provided by the S-doped carbon matrix.…”

Section: Detailed Lithium-ion Storage Mechanism Study Of α-Mns/scmfsmentioning

confidence: 89%

“…The second doublet (163.9/165.1 eV) is assigned to S atoms in the carbonaceous framework (CSC/ CS). [3,20] Finally, the broad peak located at 168.0 eV corresponds to sulfate species generated upon sample oxidation. [3,4] Taken together, the results indicate that S not only reacts with Mn atoms, but dopes the porous carbonaceous framework too.…”

Section: Synthesis and Characteristics Of α-Mns/scmfsmentioning

confidence: 99%

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Superior Lithium Storage Capacity of α‐MnS Nanoparticles Embedded in S‐Doped Carbonaceous Mesoporous Frameworks

Kim

et al. 2019

Advanced Energy Materials

124

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stability, power density, and safety. [1,3,4] Among the alternative electrode materials, transition metal sulfides (TMSs) are quite appealing due to their improved safety and high theoretical capacity (e.g., CuS: 560 mAh g −1 ; CoS 2 : 870 mAh g −1 ; and FeS 2 : 894 mAh g −1 , as calculated for the full conversion reaction). [4] Important, compared to other conversion materials, e.g., oxides, TMSs usually show improved electronic conductivity as well as faster reaction kinetics due to the weaker metal-sulfur bond (compared to the metal-oxygen bond), making the conversion reaction easier. [4] In addition, the voltage hysteresis of sulfides (≈0.7 V) is distinctly lower than that of oxides (≈0.9 V), thus promising better energy efficiencies. [5] Manganese sulfide (α-MnS) is particularly appealing as anode material for LIBs, as it possesses a large theoretical capacity (616 mAh g −1 ) and a lower redox potential compared to other TMSs, such as copper, cobalt, and iron sulfides-besides being highly abundant, ecofriendly, and less expensive. [3,6,7] Despite these advantages, the application of α-MnS as anode material in LIBs has been hampered due to common problems of TMSs such as: (i) serious volume variation during repeated (dis)charge processes leading to poor cycling stability, and (ii) low rate capability arising from low electronic conductivity and Li-ion mobility. [3,7] In order to improve the lithium-ion storage performance of TMSs, many approaches have been proposed. One of the most efficient strategies, so far, is to fabricate nano/microstructured composite materials, 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/SCMFsshows 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 Li 2 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 LiMn 1/3 Co 1/3 Ni 1/3 O 2 cathodes.

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Section: Synthesis and Characteristics Of α-Mns/scmfssupporting

confidence: 68%

Section: Detailed Lithium-ion Storage Mechanism Study Of α-Mns/scmfsmentioning

confidence: 89%

Section: Synthesis and Characteristics Of α-Mns/scmfsmentioning

confidence: 99%

See 1 more Smart Citation

Superior Lithium Storage Capacity of α‐MnS Nanoparticles Embedded in S‐Doped Carbonaceous Mesoporous Frameworks

Kim

et al. 2019

Advanced Energy Materials

124

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“…γMnS is widely used in various fields as a common semiconductor material [12]. Like NLO property of graphene-CuO, graphene-CdFe 2 O 4 , graphene-Pt, and enhanced graphene-TiO 2 , electrochemical property of graphene-γMnS was also many times higher than that of γMnS nanocrystal graphene-TiO2, electrochemical property of graphene-γMnS was also many times higher than that of γMnS nanocrystal and graphene [12][13][14]. However, there are few reports about NLO performance of graphene-γMnS.…”

Section: Introductionmentioning

confidence: 99%

“…Graphene-γMnS exhibited excellent and tunable NLO performance, illustrating that NCs materials have potential applications in NLO devices. Nanomaterials 2019, 9, 1654 2 of 16 and graphene [12][13][14]. However, there are few reports about NLO performance of graphene-γMnS.…”

mentioning

confidence: 99%

Facile One-Step Synthesis and Enhanced Optical Nonlinearity of Graphene-γMnS

Zhang

et al. 2019

Nanomaterials

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Graphene-γMnS were prepared by facile one-step hydrothermal method. Structures and properties of samples were explored by characterization, and nonlinear optical (NLO) enhancement of nanocomposites (NCs) was fully studied. Nanoparticles and NCs were tested at 532 nm by a Z-scan technique. With γMnS attached in G layers, NLO susceptibility of graphene-γMnS was greatly improved under single-pulse laser irradiation compared with G and γMnS. The nonlinearity enhanced was attributed to local field effect and charge transfer between γMnS and graphene layers. And NLO property enhancement was restricted by non-radiative defects in graphene-γMnS. Exploring the mechanism of nonlinearity enhancement was significant for fabrication of NLO devices. However, the optical nonlinearity decreased first and then increased with further increased addition of GO, because the dispersion of γMnS attached on graphene surface might make density of sp 2 fragment and defects changed. Graphene-γMnS exhibited excellent and tunable NLO performance, illustrating that NCs materials have potential applications in NLO devices. Nanomaterials 2019, 9, 1654 2 of 16 and graphene [12][13][14]. However, there are few reports about NLO performance of graphene-γMnS. In fact, we have previously studied αMnS/rGO without thoroughly investigating the nonlinearity of graphene-γMnS and the mechanism of NLO performance enhanced of NCs [15]. It is necessary to explore NLO responses of graphene-γMnS and its mechanism of enhanced nonlinearity.In this study, graphene-γMnS was synthesized by facile one-step hydrothermal method, and mechanism of NLO enhancement was discussed. Nonlinearity of NCs was controlled by changing amount of GO added, and samples were tested at 532 nm by picosecond (PS) laser pulse. We want to explore whether graphene-γMnS had potential applications in optical communication, optical limiter, and all-optical switch. Experiments Synthesis of Graphene Oxide ( GO) and Graphene-γMnSGO was prepared by improved Hummer method [16]. Firstly, graphite powder was oxidized to GO by KMnO 4 and 98% H 2 SO 4 . Then, a solution was mixed with H 2 O 2 and the mixture was washed several times with deionized water to remove impurities. Finally, products were dried at 45 • C for 48 h in vacuum drying oven. Improved Hammer method increased generation efficiency and oxidation degree of GO. Furthermore, this method could effectively prevent generation of toxic gases which caused harm to human body. High efficiency, high quality, and no toxicity in GO synthesis were important for large-scale production of GO.Graphene-γMnS was prepared by facile one-step hydrothermal method. The synthesis process of NCs was shown in Figure 1. Firstly, GO was dispersed in ethylene glycol. Secondly, TAA and MnCl 2 ·4H 2 O were added to GO suspension. After half-an-hour stirring, the solution was transferred to Teflon-lined stainless-steel autoclave and reacted at 170 • C for 6 h. The reaction temperature in our previous study was 190 • C and product was different [15]. Then, products wer...

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Shape‐Assisted 2D MOF/Graphene Derived Hybrids as Exceptional Lithium‐Ion Battery Electrodes

Jayaramulu

Dubal

Schneemann

et al. 2019

Adv Funct Materials

132

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Herein, a novel polymer‐templated strategy is described to obtain 2D nickel‐based MOF nanosheets using Ni(OH)2, squaric acid, and polyvinylpyrrolidone (PVP), where PVP has a dual role as a structure‐directing agent, as well as preventing agglomeration of the MOF nanosheets. Furthermore, a scalable method is developed to transform the 2D MOF sheets to Ni7S6/graphene nanosheet (GNS) heterobilayers by in situ sulfidation using thiourea as a sulfur source. The Ni7S6/GNS composite shows an excellent reversible capacity of 1010 mAh g−1 at 0.12 A g−1 with a Coulombic efficiency of 98% capacity retention. The electrochemical performance of the Ni7S6/GNS composite is superior not only to nickel sulfide/graphene‐based composites but also to other metal disulfide–based composite electrodes. Moreover, the Ni7S6/GNS anode exhibits excellent cycle stability (≈95% capacity retention after 2000 cycles). This outstanding electrochemical performance can be attributed to the synergistic effects of Ni7S6 and GNS, where GNS serves as a conducting matrix to support Ni7S6 nanosheets while Ni7S6 prevents restacking of GNS. This work opens up new opportunities in the design of novel functional heterostructures by hybridizing 2D MOF nanosheets with other 2D nanomaterials for electrochemical energy storage/conversion applications.

show abstract

Nanoscale α-MnS crystallites grown on N-S co-doped rGO as a long-life and high-capacity anode material of Li-ion batteries

Cited by 70 publications

References 48 publications

Superior Lithium Storage Capacity of α‐MnS Nanoparticles Embedded in S‐Doped Carbonaceous Mesoporous Frameworks

Superior Lithium Storage Capacity of α‐MnS Nanoparticles Embedded in S‐Doped Carbonaceous Mesoporous Frameworks

Facile One-Step Synthesis and Enhanced Optical Nonlinearity of Graphene-γMnS

Shape‐Assisted 2D MOF/Graphene Derived Hybrids as Exceptional Lithium‐Ion Battery Electrodes

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