Free-Standing Three-Dimensional CuCo2S4 Nanosheet Array with

Jan 8, 2019 - Encouraged by the excellent catalytic activity of this free-standing cathode, large-scale pouch-type Li–O2 cell based on CuCo2S4@Ni ca...
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Cite This: ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Free-Standing Three-Dimensional CuCo2S4 Nanosheet Array with High Catalytic Activity as an Efficient Oxygen Electrode for Lithium− Oxygen Batteries Jianping Long,† Zhiqian Hou,† Chaozhu Shu,*,†,‡ Chao Han,‡ Weijie Li,‡ Rui Huang,§ and Jiazhao Wang‡

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†

College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, 1# Dongsanlu, Erxianqiao, Chengdu 610059, Sichuan, P. R. China ‡ Institute for Superconducting and Electronic Materials, University of Wollongong, Squires Way, North Wollongong, New South Wales 2500, Australia § Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain S Supporting Information *

ABSTRACT: In this work, a novel free-standing CuCo2S4 nanosheet cathode (CuCo2S4@Ni) with high catalytic activity is fabricated for aprotic lithium−oxygen (Li−O2) battery. This deliberately designed oxygen electrode is found to yield lower overpotential (0.82 V), improved specific capacity (9673 mA h g−1 at 100 mA g−1), and enhanced cycle life (164 cycles) as compared to the traditional carbonaceous electrode. The improved performance can be ascribed to the superb spinel structure of CuCo2S4, in which both Cu and Co exhibit more abundant redox properties, improving oxygen reduction reaction and oxygen evolution reaction kinetics effectively and boosting the electrochemical reactions. Furthermore, the welldesigned architecture also plays a critical role in the improved performance. Encouraged by the excellent catalytic activity of this free-standing cathode, large-scale pouch-type Li−O2 cell based on CuCo2S4@Ni cathode is fabricated and can work under different bending and twisting conditions. This free-standing electrode provides a new strategy for developing Li−O2 batteries with excellent performance and flexible wearable devices. KEYWORDS: free-standing, CuCo2S4 nanosheet, cathode, overpotentional, Li−O2 battery reactants and accommodating discharge products.8,9 Carbonbased oxygen electrodes have initially been investigated for their high surface area and electrical conductivity as well as low cost. Meanwhile, a polymer binder was usually utilized to fix the catalyst on the carbon-based conductive agent and substrate.10−12 However, researchers have found that carbon can react with discharged product Li2O2 to form Li2CO3 and other by-products at the interface.13 The insulated and insoluble side products cause high charge overpotential, choke oxygen cathode with the battery cycling, and eventually result in cell deactivation.14−16 On the other hand, commonly used polymer binders can also be attacked by aggressive species generated during both discharge and charge processes. Irreversible side reactions caused by the decomposition of polymer binders further exacerbate battery performance.17−21

1. INTRODUCTION Energy storage systems with both high security and excellent performance are essential for the rapid development of smart grid storage systems, electric vehicles, and portable electronic devices. Rechargeable Li−O2 batteries have been considered as one of the most promising candidates for next-generation energy storage devices, thanks to their ultrahigh energy density (3500 W h kg−1).1−3 To realize the commercialization of Li− O2 battery, several key scientific and technological issues need to be addressed, including low rate capability, unsatisfied energy efficiency, and poor cyclability.4,5 These problems are closely related to the sluggish kinetics of oxygen-involved electrochemistry during discharge/charge processes.6,7 Many researchers have concentrated on the design of cathode microstructures in order to fully expose the active sites to release the potential of Li−O2 battery. For example, cathodes with high specific surface area and rationally designed pore structure demonstrated better catalytic activity because of the optimized capacity of promoting the mass transfer of © XXXX American Chemical Society

Received: September 10, 2018 Accepted: January 8, 2019 Published: January 8, 2019 A

DOI: 10.1021/acsami.8b15699 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Research Article

ACS Applied Materials & Interfaces

2.2. Synthesis of CuCo2S4@Ni Composite. CuCo2S4@Ni was synthesized by a typical hydrothermal method. Copper nitrate trihydrate (0.23 g), cobalt nitrate hexahydrate (0.56 g), thioacetamide (0.31 g), and urea (0.12 g) were added into 40 mL deionized water with continuous stirring for 2 h. The treated Ni foam was then put into the above precursor solution followed by hydrothermal treatment at 210 °C for 24 h. Finally, the CuCo2S4@Ni was obtained by drying in vacuum overnight at 50 °C. The synthesis of CuCo2S4 powder is similar to that of CuCo2S4@Ni except for the absence of Ni foam. 2.3. Material Characterizations. The microstructure and morphology of CuCo2S4@Ni composite were observed by scanning electron microscopy (SEM, Japan, JSM-6700F) and transmission electron microscopy (TEM, Japan, JEOL 2100F). X-ray diffraction (XRD, Japan) analysis was conducted on a D/MAX-IIIC powder diffractometer with Cu Kα radiation (2θ = 10−80°). X-ray photoelectron spectra (XPS) was carried out on an ESZALB 250XL spectrometer. The specific surface area and pore size distribution of CuCo2S4@Ni were determined by N2 absorption/desorption isotherms on a nitrogen adsorption analyzer (Quantachrome NOVA 1000e). 2.4. Electrochemical Performance Test. CuCo2S4@Ni was utilized as the self-standing cathode of Li−O2 cell directly. For comparison, Li−O2 cells with CuCo2S4 powder and Super P-based cathodes were also studied. The ink was prepared by dispersing CuCo2S4 powder (90 wt %) or Super P (90 wt %) and binder (polyvinylidene fluoride, 10 wt %) in N-methyl pyrrolidone. The ink was then casted on Ni foam and dried under vacuum overnight. Li− O2 cells were assembled in an argon-filled glove box (164 cycles). The excellent performance of CuCo2S4@Ni is ascribed to the superior catalytic performance of CuCo2S4 nanosheets and the deliberate design, which can avoid the formation of by-products and facilitate Li2O2

FESEM and elemental mapping images; N2 adsorption and desorption isotherms, pore size distribution; EDS data; rate performance test; EIS data; pouch-type battery test and application; recently reported results of related cathodes (PDF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Jianping Long: 0000-0001-7245-8991 Chaozhu Shu: 0000-0003-4025-0330 Jiazhao Wang: 0000-0002-1407-2166 Notes

The authors declare no competing financial interest. G

DOI: 10.1021/acsami.8b15699 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

Research Article

ACS Applied Materials & Interfaces

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ACKNOWLEDGMENTS C.S. is grateful for support from the Cultivating Program of Middle Aged Key Teachers of Chengdu University of Technology (grant no. KYGG201709) and the financial support provided by Chengdu University of Technology during his visit to the University of Wollongong.

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DOI: 10.1021/acsami.8b15699 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX