3,3′-dithiodipropionic acid as a functional electrolyte additive in lithium-sulfur battery

Abstract

High-energy-density lithium-sulfur (Li-S) batteries are among the most promising energy storage devices, but their potential has been constrained by the shuttle effect and poor active material utilization. Here, 3,3′-dithiodipropionic acid (DTPA), an efficient electrolyte additive, is applied to Li-S batteries while its underlying mechanism on the electrochemical performance is examined. The results show that the DTPA additive can quickly interact with the polysulfides scattered in the electrolyte, facilitating the conversion of long-chain polysulfides to Li₂S₂ and Li₂S. In this way, by lessening the shuttle effect of long-chain polysulfides towards the anode, the redox kinetics and the usage of active materials can both be improved. The electrochemical performance of Li-S batteries is thus enhanced by the addition of DTPA, with capacities of 1093.4 mA · h/g for the initial cycle and 714.8 mA · h/g after 250 cycles at 0.5C (DTPA concentration is 1.5 wt.%). Also, the DTPA-containing batteries have higher electrochemical stability, with a capacity retention rate of 57.5% relative to 0.1 C at 2C. The improved performance demonstrates the importance of electrolyte additives, and the DTPA introduced in this work offers a potential solution for reducing the shuttle effect of polysulfide to increase the capacity of Li-S batteries.

Keywords

lithium-sulfur battery / 3,3′-dithiodipropionic acid / polysulfide conversion / shuttle effect / electrolyte additive

References

[1] ChengJ J, LiuL F, OuS W, et al. . Sulfur/Cu_xS hybrid material for Li/S primary battery with improved discharge capacity [J]. Materials Chemistry and Physics, 2019, 224: 384-388

[2] WHITTINGHAM M S. History, evolution, and future status of energy storage [J]. Proceedings of the IEEE, 2012, 100 (Special Centennial Issue): 1518–1534. DOI: https://doi.org/10.1109/JPROC.2012.2190170.

[3] LiuJ, ZhangJ, YangZ, et al. . Materials science and materials chemistry for large scale electrochemical energy storage: From transportation to electrical grid [J]. Advanced Functional Materials, 2013, 23(8): 929-946

[4] HuangZ, LiuX-m, ZhangB, et al. . LiNi_1/3Co_1/3Mn_1/3O₂ with a novel one-dimensional porous structure: A high-power cathode material for rechargeable Li-ion batteries [J]. Scripta Materialia, 2011, 64(2): 122-125

[5] ZhaoM, LiB Q, PengH J, et al. . Lithium-sulfur batteries under lean electrolyte conditions: Challenges and opportunities [J]. Angewandte Chemie (International Ed in English), 2020, 59(31): 12636-12652

[6] BuscheM R, AdelhelmP, SommerH, et al. . Systematical electrochemical study on the parasitic shuttle-effect in lithium-sulfur-cells at different temperatures and different rates [J]. Journal of Power Sources, 2014, 259: 289-299

[7] KaiserM R, ChouS, LiuH-k, et al. . Structure-property relationships of organic electrolytes and their effects on Li/S battery performance [J]. Advanced Materials, 2017, 29(48): 1700449

[8] YueZ, DunyaH, AryalS, et al. . Synthesis and electrochemical properties of partially fluorinated ether solvents for lithiumsulfur battery electrolytes [J]. Journal of Power Sources, 2018, 401: 271-277

[9] WangY-j, MengY, ZhangZ-k, et al. . Trifunctional electrolyte additive hexadecyltrioctylammonium iodide for lithium-sulfur batteries with extended cycle life [J]. ACS Applied Materials & Interfaces, 2021, 13(14): 16545-16557

[10] KimS, KwonY M, ChoK Y, et al. . Metal iodides (LiI, MgI₂, AlI₃, TiI₄, and SnI₄) potentiality as electrolyte additives for Li - S batteries [J]. Electrochimica Acta, 2021, 391138927

[11] LiJ, HeL, QinF-r, et al. . Dual-enhancement on electrochemical performance with thioacetamide as an electrolyte additive for lithium-sulfur batteries [J]. Electrochimica Acta, 2021, 376138041

[12] LiuM-m, ChenX, ChenC, et al. . Dithiothreitol as a promising electrolyte additive to suppress the “shuttle effect” by slicing the disulfide bonds of polysulfides in lithium-sulfur batteries [J]. Journal of Power Sources, 2019, 424254-260

[13] YeH, SunJ, ZhangS, et al. . Enhanced polysulfide conversion catalysis in lithium-sulfur batteries with surface cleaning electrolyte additives [J]. Chemical Engineering Journal, 2021, 410: 128284

[14] LiJ, QinF-r, ZhangL, et al. . Mesoporous carbon from biomass: One-pot synthesis and application for Li-S batteries [J]. Journal of Materials Chemistry A, 2014, 2(34): 13916-13922

[15] LiX, YuanL, LiuD-z, et al. . Solid/quasi-solid phase conversion of sulfur in lithium-sulfur battery [J]. Small, 2022, 18(43): e2106970

[16] BrieskeD M, HassanA, WarneckeA, et al. . Modeling of the temporal evolution of polysulfide chains within the lithium-sulfur battery [J]. Energy Storage Materials, 2022, 47249-261

[17] ParkeC D, TeoL, SchwartzD T, et al. . Progress on continuum modeling of lithium-sulfur batteries [J]. Sustainable Energy & Fuels, 2021, 5(23): 5946-5966

[18] HeQ, FreibergA T S, PatelM U M, et al. . Operando identification of liquid intermediates in lithium-sulfur batteries via transmission UV-vis spectroscopy [J]. Journal of the Electrochemical Society, 2020, 167(8): 080508

[19] XiangQ, ShiC, ZhangX, et al. . Thiuram vulcanization accelerators as polysulfide scavengers to suppress shuttle effects for high-performance lithium-sulfur batteries [J]. ACS Applied Materials & Interfaces, 2019, 113329970-29977

[20] SaddM, De AngelisS, Colding-JørgensenS, et al. . Visualization of dissolution-precipitation processes in lithium-sulfur batteries [J]. Advanced Energy Materials, 2022, 12(10): 2103126

[21] MarceauH, KimC S, PaolellaA, et al. . In operando scanning electron microscopy and ultraviolet-visible spectroscopy studies of lithium/sulfur cells using all solidstate polymer electrolyte [J]. Journal of Power Sources, 2016, 319247-254

[22] SeoH K, HwaY, ChangJ H, et al. . Direct visualization of lithium polysulfides and their suppression in liquid electrolyte [J]. Nano Letters, 2020, 20(3): 2080-2086

[23] KleinM J, GoossensK, BielawskiC W, et al. . Elucidating the electrochemical activity of electrolyte-insoluble polysulfide species in lithium-sulfur batteries [J]. Journal of the Electrochemical Society, 2016, 163(9): A2109-A2116

[24] SongY-z, ZhaoW, ZhuX, et al. . Vanadium dioxide-graphene composite with ultrafast anchoring behavior of polysulfides for lithium-sulfur batteries [J]. ACS Applied Materials & Interfaces, 2018, 10(18): 15733-15741

[25] MačákM, VyroubalP, KazdaT, et al. . Numerical investigation of lithium-sulfur batteries by cyclic voltammetry [J]. Journal of Energy Storage, 2020, 27101158

[26] LiuB-r, TorresJ F, TaheriM, et al. . Dual-ion flux management for stable high areal capacity lithium-sulfur batteries [J]. Advanced Energy Materials, 2022, 12(10): 2103444

[27] CaiD, GaoY, WangX, et al. . Built-In electric field on the mott-schottky heterointerface-enabled fast kinetics lithium-sulfur batteries [J]. ACS Applied Materials & Interfaces, 2022, 143438651-38659

[28] ZhangZ-j, YangY, GuoW, et al. . Synergistic capture and conversion of soluble polysulfides in Li-S batteries with composite freestanding carbonaceous interlayers [J]. ACS Applied Materials & Interfaces, 2022, 14(7): 9231-9241

[29] ShiC, HongB, ZhangX, et al. . In-situ growth poly(N-methylaniline) coating on sulfur cathode for lithium-sulfur battery [J]. Journal of Electroanalytical Chemistry, 2020, 871114312

[30] VuD L, KimN, MyungY, et al. . Aluminum phosphate as a bifunctional additive for improved cycling stability of Li-S batteries [J]. Journal of Power Sources, 2020, 459228068

[31] ZhaoM, PengH-j, WeiJ, et al. . Dictating high-capacity lithium-sulfur batteries through redox-mediated lithium sulfide growth (small methods 6/2020) [J]. Small Methods, 2020, 4(6): 2070020

[32] WangZ, LiuJ, ZhangB, et al. . Modulating molecular orbital energy level of lithium polysulfide for highrate and long-life lithium-sulfur batteries [J]. Energy Storage Materials, 2020, 24373-378

[33] Sanchis-GualR, Seijas-Da SilvaA, Coronado-PuchauM, et al. . Improving the onset potential and Tafel slope determination of earth-abundant water oxidation electrocatalysts [J]. Electrochimica Acta, 2021, 388138613

[34] ChenH, ElliottJ R, LeH-n, et al. . Super-Nernstian Tafel slopes: An origin in coupled homogeneous kinetics [J]. Journal of Electroanalytical Chemistry, 2020, 869114185

[35] QiuX, HuaQ-s, ZhengL, et al. . Study of the discharge/charge process of lithium-sulfur batteries by electrochemical impedance spectroscopy [J]. RSC Advances, 2020, 10(9): 5283-5293

[36] Drvarič TalianS, MoškonJ, DominkoR, et al. . The pitfalls and opportunities of impedance spectroscopy of lithium sulfur batteries [J]. Advanced Materials Interfaces, 2022, 9(8): 2101116

[37] LiuY, PanY-z, BanJ, et al. . Promoted rate and cycling capability of Li-S batteries enabled by targeted selection of co-solvent for the electrolyte [J]. Energy Storage Materials, 2020, 25131-136

[38] LiJ, ZhangL, QinF-r, et al. . ZrO(NO₃)₂ as a functional additive to suppress the diffusion of polysulfides in lithium - Sulfur batteries [J]. Journal of Power Sources, 2019, 442227232

[39] MukraT, HorowitzY, ShekhtmanI, et al. . Disiloxane with nitrile end groups as Co-solvent for electrolytes in lithiumsulfur batteries - A feasible approach to replace LiNO₃ [J]. Electrochimica Acta, 2019, 30776-82

[40] ChuH, NohH, KimY J, et al. . Achieving three-dimensional lithium sulfide growth in lithium-sulfur batteries using high-donor-number anions [J]. Nature Communications, 2019, 10188

[41] LinY, ChenD, WangS-j, et al. . Addressing passivation of a sulfur electrode in Li-S pouch cells for dramatically improving their cyclic stability [J]. ACS Applied Materials & Interfaces, 2020, 12(26): 29296-29301

[42] YangW, YangW, SunB, et al. . Mixed lithium oxynitride/oxysulfide as an interphase protective layer to stabilize lithium anodes for high-performance lithium-sulfur batteries [J]. ACS Applied Materials & Interfaces, 2018, 10(46): 39695-39704

[43] GuS, JinJ, ZhuoS-j, et al. . Organic polysulfides based on −S −S −S − structure as additives or cosolvents for high performance lithium-sulfur batteries [J]. Chem Electro Chem, 2018, 5(13): 1717-1723

[44] LiuY, LiB, LiuJ, et al. . Pre-planted nucleation seeds for rechargeable metallic lithium anodes [J]. Journal of Materials Chemistry A, 2017, 5(35): 18862-18869

[45] XieP-f, ZhangB, ZhouY-k, et al. . A dual-coated multifunctional separator for the high-performance lithium-sulfur batteries [J]. Electrochimica Acta, 2021, 395139181

[46] MaG, WenZ, WuM-f, et al. . A lithium anode protection guided highly-stable lithium-sulfur battery [J]. Chemical Communications, 2014, 50(91): 14209-14212