Abstract
Practical application of Li-S battery is limited by the fast capacity decay and low coulombic efficiency caused by the shuttling phenomenon. Modification of the battery separator to impart the separator with ionic sieving property is an effective strategy to alleviate the shuttling phenomenon. In this study, perfluorinated sulfonic acid (PFSA) ionomers with different equivalent weight (EW) values are used to modify the commercial polyethylene separator, and the electrochemical performance of these separators is systematically investigated. Our results show that the separator modified using PFSA ionomer with a low EW value of 830 shows optimal battery performance owing to its unique structure of the ionic cluster. The Li-S battery with this modified separator shows an initial discharge capacity of 1352 mAh g−1 and a retained capacity of 931.6 mAh g−1 after cycling 100 times at 0.2 C, which demonstrates the effectiveness of this modification strategy. Furthermore, the correlation between the properties of PFSA ionomers and the electrochemical performance of the modified separator unveiled in this study may provide insight for the rational design of advanced separator for battery applications.
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References
Wang ZY, Wang L, Liu S, Li GR, Gao XP (2019) Conductive CoOOH as carbon-free sulfur immobilizer to fabricate sulfur-based composite for lithium–sulfur battery. Adv Funct Mater:1901051
Bauer I, Thieme S, Brückner J, Althues H, Kaskel S (2014) Reduced polysulfide shuttle in lithium–sulfur batteries using Nafion-based separators. J Power Sources 251:417–422
Conder J, Urbonaite S, Streich D, Novák P, Gubler L (2015) Taming the polysulphide shuttle in Li–S batteries by plasma-induced asymmetric functionalisation of the separator. RSC Adv 5(97):79654–79660
Kim SH, Yeon JS, Kim R, Choi KM, Park HS (2018) A functional separator coated with sulfonated metal–organic framework/Nafion hybrids for Li–S batteries. J Mater Chem A 6(48):24971–24978
Li Z, Han Y, Wei J, Wang W, Cao T, Xu S, Xu Z (2017) Suppressing shuttle effect using Janus cation exchange membrane for high-performance lithium-sulfur battery separator. ACS Appl Mater Interfaces 9(51):44776–44781
Gao J, Sun C, Xu L, Chen J, Wang C, Guo D, Chen H (2018) Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode. J Power Sources 382:179–189
Huang J, Sun Y, Wang Y, Zhang Q (2017) Review on advanced functional separators for lithium-sulfur batteries. Acta Chim Sin 75(2):173
Xiang Y, Li J, Lei J, Liu D, Xie Z, Qu D, Li K, Deng T, Tang H (2016) Advanced separators for lithium-ion and Lithium-sulfur batteries: a review of recent progress. ChemSusChem 9(21):3023–3039
Lin W, Chen Y, Li P, He J, Zhao Y, Wang Z, Liu J, Qi F, Zheng B, Zhou J, Xu C, Fu F (2015) Enhanced performance of lithium sulfur battery with a reduced graphene oxide coating separator. J Electrochem Soc 162(8):A1624–A1629
Zhou G, Pei S, Li L, Wang DW, Wang S, Huang K, Yin LC, Li F, Cheng HM (2014) A graphene-pure-sulfur sandwich structure for ultrafast, long-life lithium-sulfur batteries. Adv Mater 26(4):625–631 664
Bai S, Liu X, Zhu K, Wu S, Zhou H (2016) Metal–organic framework-based separator for lithium–sulfur batteries. Nat Energy 1(7)
Wu F, Qian J, Chen R, Ye Y, Sun Z, Xing Y, Li L (2016) Light-weight functional layer on a separator as a polysulfide immobilizer to enhance cycling stability for lithium–sulfur batteries. J Mater Chem A 4(43):17033–17041
Zhang Z, Li X, Yan Y, Zhu W, Shao LH, Li J (2019) A bioinspired functionalization of polypropylene separator for lithium-sulfur battery. Polymers (Basel) 11(4)
Zhang Z, Lai Y, Zhang Z, Zhang K, Li J (2014) Al2O3-coated porous separator for enhanced electrochemical performance of lithium sulfur batteries. Electrochim Acta 129:55–61
Wei H, Ma J, Li B, Zuo Y, Xia D (2014) Enhanced cycle performance of lithium-sulfur batteries using a separator modified with a PVDF-C layer. ACS Appl Mater Interfaces 6(22):20276–20281
Chung S-H, Han P, Singhal R, Kalra V, Manthiram A (2015) Electrochemically stable rechargeable lithium-sulfur batteries with a microporous carbon nanofiber filter for polysulfide. Adv Energy Mater 5(18)
Cheng X, Wang W, Wang A, Yuan K, Jin Z, Yang Y, Zhao X (2016) Oxidized multiwall carbon nanotube modified separator for high performance lithium–sulfur batteries with high sulfur loading. RSC Adv 6(92):89972–89978
Chang C-H, Chung S-H, Manthiram A (2015) Ultra-lightweight PANiNF/MWCNT-functionalized separators with synergistic suppression of polysulfide migration for Li–S batteries with pure sulfur cathodes. J Mater Chem A 3(37):18829–18834
Balach J, Jaumann T, Klose M, Oswald S, Eckert J, Giebeler L (2016) Improved cycling stability of lithium–sulfur batteries using a polypropylene-supported nitrogen-doped mesoporous carbon hybrid separator as polysulfide adsorbent. J Power Sources 303:317–324
Qiu W, An C, Yan Y, Xu J, Zhang Z, Guo W, Wang Z, Zheng Z, Wang Z, Deng Q, Li J (2019) Suppressed polysulfide shuttling and improved Li+ transport in Li S batteries enabled by NbN modified PP separator. J Power Sources 423:98–105
Yang X, Qian X, Jin L, Yao S, Rao D, Shen X, Wang L, Tan J (2018) Separator modified with Ketjenblack-In2O3 nanoparticles for long cycle-life lithium-sulfur batteries. J Solid State Electrochem 23(2):645–656
Cai W, Li G, He F, Jin L, Liu B, Li Z (2015) A novel laminated separator with multi functions for high-rate dischargeable lithium–sulfur batteries. J Power Sources 283:524–529
Hao Z, Yuan L, Li Z, Liu J, Xiang J, Wu C, Zeng R, Huang Y (2016) High performance lithium-sulfur batteries with a facile and effective dual functional separator. Electrochim Acta 200:197–203
Zhuang TZ, Huang JQ, Peng HJ, He LY, Cheng XB, Chen CM, Zhang Q (2016) Rational integration of polypropylene/graphene oxide/Nafion as ternary-layered separator to retard the shuttle of polysulfides for lithium-sulfur batteries. Small 12(3):381–389
Jin Z, Xie K, Hong X, Hu Z, Liu X (2012) Application of lithiated Nafion ionomer film as functional separator for lithium sulfur cells. J Power Sources 218:163–167
Yu X, Joseph J, Manthiram A (2015) Polymer lithium-sulfur batteries with a Nafion membrane and an advanced sulfur electrode. J Mater Chem A 3(30):15683–15691
Hencz L, Chen H, Ling HY, Wang Y, Lai C, Zhao H, Zhang S (2019) Housing sulfur in polymer composite frameworks for Li–S batteries. Nano-Micro Lett 11(1):17
Li G, Wang C, Cai W, Lin Z, Li Z, Zhang S (2016) The dual actions of modified polybenzimidazole in taming the polysulfide shuttle for long-life lithium–sulfur batteries. NPG Asia Mater 8(10):e317–e317
Chen H, Ling M, Hencz L, Ling HY, Li G, Lin Z, Liu G, Zhang S (2018) Exploring chemical, mechanical, and electrical functionalities of binders for advanced energy-storage devices. Chem Rev 118(18):8936–8982
Vishnyakov A, Neimark AV (2014) Self-assembly in Nafion membranes upon hydration: water mobility and adsorption isotherms. J Phys Chem B 118(38):11353–11364
Gebel G, Moore RB (2000) Small-angle scattering study of short pendant chain perfuorosulfonated ionomer membranes. Macromolecules 33(13):4850–4855
Cai W, Li G, He F, Jin L, Liu B, Li Z (2015) A novel laminated separator with multi functions for high-rate dischargeable lithium-sulfur batteries. J Power Sources 283:524–529
Zhao B, Zhang Z, Wang Y, Jin Y, Gao H (2019) A novel type of multifunctional binder for improved cycle stability of lithium-sulfur battery. J Solid State Electrochem 23(4):1269–1278
Huang J-Q, Zhang Q, Peng H-J, Liu X-Y, Qian W-Z, Wei F (2014) Ionic shield for polysulfides towards highly-stable lithium–sulfur batteries. Energy Environ Sci 7(1):347–353
T-L HO (1975) The hard soft acids bases (HSAB) principle and organic chemistry. Chem Rev 75(1):1–20
He G, Evers S, Liang X, Cuisinier MG, A., Nazar LF (2013) Tailoring porosity in carbon nanospheres for lithium–sulfur battery cathodes. ACS Nano 7 (12):10920–10930
Zeng F, Jin Z, Yuan K, Liu S, Cheng X, Wang A, Wang W, Yang Y-s (2016) High performance lithium–sulfur batteries with a permselective sulfonated acetylene black modified separator. J Mater Chem A 4(31):12319–12327
Babu DB, Giribabu K, Ramesha K (2018) Permselective SPEEK/Nafion composite-coated separator as a potential polysulfide crossover barrier layer for Li-S batteries. ACS Appl Mater Interfaces 10(23):19721–19729
Pan H, Tan Z, Zhou H, Jiang L, Huang Z, Feng Q, Zhou Q, Ma S, Kuang Y (2019) Fe3C-N-doped carbon modified separator for high performance lithium-sulfur batteries. J Energy Chem 39:101–108
Peng H-J, Zhang Z-W, Huang J-Q, Zhang G, Xie J, Xu W-T, Shi J-L, Chen X, Cheng X-B, Zhang Q (2016) A cooperative interface for highly efficient lithium-sulfur batteries. Adv Mater 28(43):9551–9558
Al Salem H, Babu G, V. Rao C, Arava LMR (2015) Electrocatalytic polysulfide traps for controlling redox shuttle process of Li–S batteries. J Am Chem Soc 137 (36):11542–11545
Liang X, Kwok CY, Lodi-Marzano F, Pang Q, Cuisinier M, Huang H, Hart CJ, Houtarde D, Kaup K, Sommer H, Brezesinski T, Janek J, Nazar LF (2016) Tuning transition metal oxide-sulfur interactions for long life lithium sulfur batteries: the “goldilocks” principle. Adv Energy Mater 6(6):1501636
Zhao M, Peng HJ, Zhang ZW, Li BQ, Chen X, Xie J, Chen X, Wei JY, Zhang Q, Huang JQ (2019) Activating inert metallic compounds for high-rate lithium-sulfur batteries through in situ etching of extrinsic metal. Angew Chem Int Ed Engl 58(12):3779–3783
Zhang X-Q, Chen X, Hou L-P, Li B-Q, Cheng X-B, Huang J-Q, Zhang Q (2019) Regulating anions in the solvation sheath of lithium ions for stable lithium metal batteries. ACS Energy Lett 4(2):411–416
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This work was financially supported by the National Natural Science Foundation of China (51976143). We acknowledge the Material Research and Characterization Center at WHUT.
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Jiao, J., Li, H., Lin, W. et al. Rational design of perfluorinated sulfonic acid ionic sieve modified separator for high-performance Li-S battery. J Solid State Electrochem 24, 771–779 (2020). https://doi.org/10.1007/s10008-020-04503-7
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DOI: https://doi.org/10.1007/s10008-020-04503-7