The synergistic effect of nickel cobalt sulfide nanoflakes and sulfur-doped porous carboneous nanostructure as bifunctional electrocatalyst for enhanced rechargeable Li-O2 batteries

Hyun, Suyeon; Son, Byungrak; Kim, Hasuck; Sanetuntikul, Jakkid; Shanmugam, Sangaraju

doi:10.1016/j.apcatb.2019.118283

Cited by 61 publications

(34 citation statements)

References 56 publications

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“…[42,43] After recharging, these diffraction peaks associated with Li 2 O 2 are completely removed, implying that the formation and decomposition of Li 2 O 2 are highly reversible on NiO@Ni 2 P. [44] On the contrary, the LiOH phase is detected on the discharged NiO (Figure S10a, Supporting Information) and Ni 2 P electrodes (Figure S10b, Supporting Information), which may derive from the parasitic reaction on these two electrodes. [45] The formation of LiOH will cause an increase in the charging potential, resulting in a poor rechargeability. In addition, the Raman and XPS results of the NiO@Ni 2 P electrode also show that the product after discharging is mainly Li 2 O 2 and is completely decomposed after charging, further illustrating the excellent reversibility of the NiO@Ni 2 P electrode (Figure 7b-d).…”

Section: Resultsmentioning

confidence: 99%

Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni₂P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Yan

Ran

Zeng

et al. 2022

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ultimately increasing the charge transfer resistance. [8] During the OER process, the insulated Li 2 O 2 can only be decomposed at high overpotential, which can trigger severe parasitic reactions. [9][10][11] Therefore, exploring efficient bifunctional electrocatalysts and understanding the formation and decomposition mechanism of Li 2 O 2 is of great significance for effectively reducing ORR and OER overpotential and improving the electrochemical performance of LOBs.Currently, two types of mechanisms (solution-mediated pathway and surface adsorption pathway) were commonly recommended to explain the deposition process of Li 2 O 2 on the electrode surface during ORR. Different mechanisms lead to various structure (crystallinity or defect) and morphology (toroid or thin film) of Li 2 O 2 , eventually determining the battery performance. [12] For the solution-mediated pathway, disproportionation reaction of dissolved intermediate LiO 2 usually forms a large-size toroid-like Li 2 O 2 , resulting in a large discharge capacity but a high charge overpotential which is due to the limited contact between large-size discharge products and electrode surface. [3,12] For the surface adsorption pathway, electrode surface shows strong adsorption toward intermediate LiO 2 , finally leading to the deposition of thin film-like amorphous Li 2 O 2 on the oxygen electrode. The thin film-like Li 2 O 2 is in close contact with electrode, which is beneficial to reduce the charging overpotential. However, film-like discharge product will deliver a small discharge capacity because of the quickly passivated electrode surface. [13] As a result, designing porous oxygen electrodes with tuned adsorption capacity towards O-containing intermediates is essential for LOBs with both large discharge capacity and small charge overpotential. Generally, regulating the heterogeneous interfaces in the catalytic materials to realize the electronic modulation through interfacial coupling has proved to be an effective strategy for optimizing the chemical adsorption of the O-containing intermediates and accelerating the kinetics of oxygen electrode reactions. [14][15][16] Specifically, to achieve the thermodynamic equilibrium state, two regions of opposing charge distribution and a built-in electric field will be created at the interface of the heterostructure, where the strong charge region can modulate the adsorption of reactant, while the built-in Lithium-oxygen batteries (LOBs) with ultra-high theoretical energy density (≈3500 Wh kg −1 ) are considered as the most promising energy storage systems. However, the sluggish kinetics during the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) can induce large voltage hysteresis, inferior roundtrip efficiency and unsatisfactory cyclic stability. Herein, hydrangea-like NiO@Ni 2 P heterogeneous microspheres are elaborately designed as high-efficiency oxygen electrodes for LOBs. Benefitting from the interfacial electron redistribution on NiO@Ni 2 P heterostructure, the electronic structure can b...

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Section: Resultsmentioning

confidence: 99%

Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni₂P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Yan

Ran

Zeng

et al. 2022

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“…Commonly, due to the insulation and insolubilization characteristics of Li 2 CO 3 accumulations as well as the unsatisfactory electrochemical catalytic decomposition capability of Ti 3 C 2 SQD/N-C and Ti 3 C 2 MNS/N-C, the readily available active sites would drastically fade due to the increased dead space by Li 2 CO 3 coverage, ultimately leading to cell failure. [9] Then the geometrical morphology and electronic structure of Ti 3 C 2 QDC/N-C catalyst after 200 cycles are carefully examined. As shown in the TEM, SAED, and element mapping images in Figure S26a-c (Supporting Information), the robust Ti 3 C 2 QDC building blocks are still uniformly distributed throughout the N-C scaffold without apparent agglomeration.…”

Section: Ex Situ Investigation After Discharge and Chargementioning

confidence: 99%

“…with synergistically tailored geometric constructions and electronic characteristics to manipulate Li 2 O 2 accommodations with optimized morphology and structure. [8][9][10][11][12] As a future-proof approach, seeking for efficient catalysts is still a rigorous challenge for Li-O 2 chemistry. In response, defect engineering (vacancies, edges, boundaries, dislocations, and doping) shows huge potential in tuning the electronic structure and thus facilitates the electrochemical characteristic of active catalysts.…”

mentioning

confidence: 99%

Bifunctional Catalytic Activity Guided by Rich Crystal Defects in Ti₃C₂ MXene Quantum Dot Clusters for Li–O₂ Batteries

Wang

Zhao

Hui

et al. 2021

Advanced Energy Materials

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lithium-ion counterparts. This technologically favorable Li-O 2 battery works on the following principle: 2Li + + O 2 + 2e -⇔Li 2 O 2 (2.96 V), involving with oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) processes, respectively. [1][2][3] Despite admitted competitiveness, there still exists serious bottleneck and key scientific issues to be solved. Cumbersome overpotential and thereby induced detrimental parasitic reaction during repeated cycles cast a shadow over the real-life implementation of Li-O 2 batteries. In terms of cathode side, solid discharge species, namely Li 2 O 2 , with inherent poor conductivity and insolubility in electrolyte, are tough to be decomposed. Intrinsically, electrochemical reaction kinetics is undesirably retarded, giving rise to large potential hysteresis between ORR and OER. [4][5][6][7] To circumvent this notorious dilemma, the prevailing strategy lies on the exploitation of efficient catalysts (precious metals, carbonaceous materials, metallic oxides, sulfides, etc.) with synergistically tailored geometric constructions and electronic characteristics to manipulate Li 2 O 2 accommodations with optimized morphology and structure. [8][9][10][11][12] As a future-proof approach, seeking for efficient catalysts is still a rigorous challenge for Li-O 2 chemistry. In response, defect engineering (vacancies, edges, boundaries, dislocations, and doping) shows huge potential in tuning the electronic structure and thus facilitates the electrochemical characteristic of active catalysts. [13][14][15] For instance, J. O-Medina et al. demonstrated that the defective sites such as, heteroatom doping, vacancies, and edges could tailor the initial sp 2 -hybridized networks of nanocarbons, leading to enhancement of electrocatalysis activity. [16] Wang's group also proposed that the introduction of various defects played a crucial role in modifying electron delocalization structure within carbon and metallic compounds for various rechargeable batteries, suggesting its superiority in accelerating charge transfer kinetics and optimizing intermediate adsorption behavior during cycling. [13] Wang et al. reported that superior catalytic activity and long-term stability towards electrocatalytic reactions could be realized by introducing doping, edge, and grain boundary defects. [14] Ameliorating round-trip efficiency and mitigating parasitic reaction play a key role in enhancing the activity and durability of lithium-oxygen batteries. Herein, it is first reported that Ti 3 C 2 MXene quantum dot clusters full of rich crystal defects anchored on N-doped carbon nanosheets (Ti 3 C 2 QDC/N-C) can operate well as bifunctional catalyst for Li-O 2 batteries. The well-defined grain boundary and edge defects make crucial contributions in modulating the local unsaturated coordination state of active titanium atoms and thus the electronic structure of Ti 3 C 2 QDC/N-C, greatly enhancing the catalytic capability. Furthermore, density functional theory calculations disclose that the fruitful cryst...

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“…After 60th charging, the charge transfer resistance slightly increased, indicating the excellent cycling performance of MnCo 2 S 4 -CoS 1.097 cathodes. In addition, compared with the most of the reported typical sulfides [46][47][48][49][50][51][52][53] and noble metals based cathodes (Figure 3h), [54][55][56][57][58][59][60][61][62] it is worth mentioning that the MnCo 2 S 4 -CoS 1.097 cathode deliver superior cycling stability under similar testing conditions.…”

Section: Resultsmentioning

confidence: 99%

MnCo₂S₄‐CoS_1.097 Heterostructure Nanotubes as High Efficiency Cathode Catalysts for Stable and Long‐Life Lithium‐Oxygen Batteries Under High Current Conditions

et al. 2021

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Constructing the heterostructures is considered to be one of the most effective methods to improve the poor electrical conductivity and insufficient electrocatalytic properties of metal sulfide catalysts. In this work, MnCo 2 S 4 -CoS 1.097 nanotubes are successfully prepared via a refluxhydrothermal process. This novel cathode catalyst delivers high discharge/charge specific capacities of 21 765/21 746 mAh g −1 at 200 mA g −1 and good rate capability. In addition, a favorable cycling stability with a fixed specific capacity of 1000 mAh g −1 at high current density of 1000 mA g −1 (167 cycles) and 2000 mA g −1 (57 cycles) are delivered. It is proposed that fast transmission of ions and electrons accelerated by the built-in electric field, multiple active sites from the heterostructure, and nanotube architecture with large specific surface area are responsible for the superior electrochemical performance. To some extent, the rational design of this heterostructured metal sulfide catalyst provides guidance for the development of the stable and efficient cathode catalysts for Li-O 2 batteries that can be employed under high current conditions.

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The synergistic effect of nickel cobalt sulfide nanoflakes and sulfur-doped porous carboneous nanostructure as bifunctional electrocatalyst for enhanced rechargeable Li-O2 batteries

Cited by 61 publications

References 56 publications

Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni₂P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni₂P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Bifunctional Catalytic Activity Guided by Rich Crystal Defects in Ti₃C₂ MXene Quantum Dot Clusters for Li–O₂ Batteries

MnCo₂S₄‐CoS_1.097 Heterostructure Nanotubes as High Efficiency Cathode Catalysts for Stable and Long‐Life Lithium‐Oxygen Batteries Under High Current Conditions

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The synergistic effect of nickel cobalt sulfide nanoflakes and sulfur-doped porous carboneous nanostructure as bifunctional electrocatalyst for enhanced rechargeable Li-O2 batteries

Cited by 61 publications

References 56 publications

Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni2P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni2P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Bifunctional Catalytic Activity Guided by Rich Crystal Defects in Ti3C2 MXene Quantum Dot Clusters for Li–O2 Batteries

MnCo2S4‐CoS1.097 Heterostructure Nanotubes as High Efficiency Cathode Catalysts for Stable and Long‐Life Lithium‐Oxygen Batteries Under High Current Conditions

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Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni₂P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Interfacial Electron Redistribution of Hydrangea‐like NiO@Ni₂P Heterogeneous Microspheres with Dual‐Phase Synergy for High‐Performance Lithium–Oxygen Battery

Bifunctional Catalytic Activity Guided by Rich Crystal Defects in Ti₃C₂ MXene Quantum Dot Clusters for Li–O₂ Batteries

MnCo₂S₄‐CoS_1.097 Heterostructure Nanotubes as High Efficiency Cathode Catalysts for Stable and Long‐Life Lithium‐Oxygen Batteries Under High Current Conditions