Letter Cite This: ACS Appl. Energy Mater. 2018, 1, 932−940
www.acsaem.org
Novel Synergistic Strategy for Developing High-Performance Lithium Sulfur Batteries of Large Areal Sulfur Loading by SEI Modified Separator Junling Guo, Shupeng Zhao, Gaohong He, and Fengxiang Zhang*
ACS Appl. Energy Mater. 2018.1:932-940. Downloaded from pubs.acs.org by KAOHSIUNG MEDICAL UNIV on 11/06/18. For personal use only.
State Key Laboratory of Fine Chemicals and School of Petroleum and Chemical Engineering, Dalian University of Technology, 2 Dagong Road, Liaodongwan New District, Panjin 124221, People’s Republic of China S Supporting Information *
ABSTRACT: As a crucial energy density determining factor, the areal sulfur loading is still low nowadays for practical applications of Li−S batteries. To address this issue, intensive research efforts have been devoted to development of sulfur-hosting materials with ultrahigh specific surface area. However, design and manufacturing processes for these materials are complicated. Herein, we report a novel and facile strategy for developing a high-performance cathode with high areal sulfur content using conventional sulfur hosts without ultrahigh specific area. This strategy features a dense blocking layer of solid electrolyte interface (SEI) on the separator to ensure cycle stability of the cathode with a high areal sulfur loading. Meanwhile, a nanoarray cathode structure (CNT array on carbon cloth) is adopted to guarantee high sulfur utilization and rate performance. With the synergistic effect of a dense blocking layer and CNT array structure, the cathode with 10 mg/cm2 sulfur (90.9% in CNT/S composite) shows good rate and cycle performance. Our strategy may open up a new avenue for the design and construction of superior Li−S batteries with large sulfur loading without complex materials synthesis. KEYWORDS: Li−S battery, solid electrolyte interface, CNT array, large areal sulfur loading, separator
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interactions so that a good cycle stability can be achieved.13−15 High surface area is also needed for immobilizing insoluble Li2S2 or Li2S16,17 to ensure a high sulfur utilization and rate performance; without adequate surface area, a thick Li2S2 or Li2S layer will deposit on the hosting materials, impede subsequent reactions of PS, and reduce the holistic electrical conductivity of the electrode.18,19 However, if the sulfur content is too high, much surface area will be lost and become unavailable for polysulfide trapping and Li2S2 or Li2S immobilization. In the past few years, intensive research efforts have been made to develop sulfur hosts with ultrahigh specific surface area.20−22 Through these efforts, the sulfur mass content and areal loading can be increased to 90% and >6 mg/cm2, respectively.23,24 However, the complexity involved in the design and manufacturing process for these materials is not compatible with practical application of the battery.11 Therefore, it is highly desired to design and fabricate a cathode of large areal sulfur loading without involvement of complex sulfur hosts synthesis.
i−S batteries have been regarded as one of the most promising candidates for next-generation batteries since their theoretical energy density (∼2,600 Wh/kg) is much higher than that of existing lithium-ion batteries (∼200 Wh/ kg).1,2 However, there are some drawbacks impeding their popularization, including low sulfur utilization due to its low electrical conductivity and unsatisfactory cycle performance caused by “redox shuttle reactions” of dissolved lithium polysulfides (PSs).3,4 These issues have been addressed in many previous works; however, the areal sulfur loading, as a crucial factor related to the energy density of the batteries, is still low (15 mg/cm2), the batteries cannot be charged− discharged properly when the current density is higher than 0.5 C. Since our synergistic strategy can guarantee high sulfur loading and high rate performance simultaneously, the Li−S battery could drive a miniature 30−200 rpm rotation motor (see Video S1) very easily. In summary, we have developed a novel strategy for constructing high-performance cathodes with large areal loading of sulfur. Differing from the conventional methodology of trapping dissolved polysulfide with ultrahigh specific area hosting materials, we simply decorated the separator with a dense layer of SEI to confine dissolved polysulfide between the cathode and the separator; this guarantees the cycle stability of the cathode with a large sulfur loading. Meanwhile, we adopted an array structure for the cathode to ensure a good rate performance of the cathode with a large sulfur loading. Attributed to the above synergistic strategy, our battery exhibits an ultrahigh areal specific capacity of 12.2 mAh/cm2, a high rate performance (1221 mAh/g at 0.1 C, 1096 mAh/g at 0.2 C, 929 mAh/g at 0.5 C, 752 mAh/g at 1 C, and 400 mAh/g at 2 C, respectively), and good cycle stability (88% capacity retention after 100 cycles at 0.5 C). Our work will open up a new avenue for the facile construction of high-performance sulfur cathodes with large areal loading.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsaem.7b00290. (Figure S1) TEM images; (Figure S2) SEM images; (Figures S3) TGA curve; (Figures S4) charge-dicharge curve within 1.8−3 V; (Figures S5) cross-section SEM and diffusion test; (Figures S6 and S7) SEM and performance of different coated separators; (Figure S8) cycle performance; (Table S1) performance comparison (PDF) (Video S1) Mini rotation motor driven by Li−S battery (AVI)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Gaohong He: 0000-0002-6674-8279 Fengxiang Zhang: 0000-0002-3793-6860 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work was supported by grants from the Fund of the State Key Laboratory of Fine Chemicals Panjin (Grant No. JH2014009), the National Natural Science Foundation of China (Grant Nos. 21276252 and 21776042), and China MOST (Ministry of Science and Technology) innovation team in key areas (Grant No. 2016RA4053).
EXPERIMENTAL METHODS
Materials Preparation. Carbon Black-, Carbon Sphere- and Li4Ti5O12-Coated Separators. A homogeneous slurry was prepared by mixing the carbon black or carbon sphere or Li4Ti5O12 with poly(vinylidene difluoride) binder (8:2 by weight) in the presence of N-methyl-2-pyrrolidone. The slurry was then cast on a polypropylene membrane and heated at 60 °C for 12 h under vacuum. CNT Array on Carbon Cloth. A piece of carbon cloth (CC; 2 cm × 2 cm) was immersed into a precursor solution and kept for 1 h. The precursor solution was prepared by dissolving 0.025 mol of nickel nitrate hexahydrate in a 50 mL mixed solution of alcohol and ethylene glycol (1:1, v/v) under stirring. After being dried in ambient air, the treated CC was heated in a tube furnace for 1 h at 800 °C under a flowing N2 atmosphere with an 18 mL mixed solution of ethanol and ethylene glycol (1:5, v/v) placed upstream. Li2S8 Electrolyte. The Li2S8 electrolyte (0.2 M) was prepared by dissolving stoichiometric amounts of Li2S (195 mg), sulfur (945 mg), lithium bis(trifluoromethanesulfone) imide (LiTFSI, 1 M), and LiNO3 (2 wt %) in a mixture (21 mL) of 1,3-dioxolane/1,2-dimethoxyethane (DOL/DME) with a volume ratio of 1:1. Materials Characterizations. The morphologies of the asprepared separators were studied using an FEI NanoSEM-450 Nova
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DOI: 10.1021/acsaem.7b00290 ACS Appl. Energy Mater. 2018, 1, 932−940
