Tailoring Li₂CO₃ configuration and orbital structure of CoS to improve catalytic activity and stability for Li-CO₂ batteries

Abstract

The sluggish reaction kinetics has greatly hampered the development of reversible Li-CO₂ batteries. Especially during charge, high charge voltage and possible side reactions during Li₂CO₃ decomposition require both high activity and strong durability of catalysts. Herein, a strategy of introducing rich sulfur vacancies is proposed, which tailors the configuration of Li₂CO₃ and the orbital structure of CoS to realize the dual enhancement. The calculation results show that charge redistribution by sulfur vacancies on the catalyst stretches the adsorbed Li₂CO₃ and consequently facilitates its decomposition. Moreover, the induced vacancies lower the S 2p band center, promoting the electrochemical stability of sulfides. Therefore, Li-CO₂ batteries with sulfur vacancy-rich CoS exhibit a low overpotential of 1.07 V after 400 h cycling, while batteries with pristine CoS have a short lifespan that the overpotential exceeds 1.75 V after cycling for 200 h. This study not only proposes a strategy to improve both catalytic activity and stability but also paves new avenues for designing advanced catalysts for Li-CO₂ batteries and beyond.

Keywords

catalyst / Li-CO₂ batteries / stability / sulfur vacancy

References

[1] Fetrow CJ, Carugati C, Zhou X-D, Wei S. Electrochemistry of metal-CO₂ batteries: opportunities and challenges. Energy Storage Mater. 2022;45:911-933.

[2] Sarkar A, Dharmaraj VR, Yi CH, et al. Recent advances in rechargeable metal–CO₂ batteries with nonaqueous electrolytes. Chem Rev. 2023;123(15):9497-9564.

[3] Wunderling N, Winkelmann R, Rockström J, et al. Global warming overshoots increase risks of climate tipping cascades in a network model. Nat Clim Chang. 2023;13(1):75-82.

[4] Qiao Y, Yi J, Wu S, et al. Li-CO₂ electrochemistry: a new strategy for CO₂ fixation and energy storage. Joule. 2017;1(2):359-370.

[5] Zhang Z, Bai W-L, Wang K-X, Chen J-S. Electrocatalyst design for aprotic Li–CO₂ batteries. Energy Environ Sci. 2020;13(12):4717-4737.

[6] Liu B, Sun Y, Liu L, et al. Recent advances in understanding Li–CO₂ electrochemistry. Energy Environ Sci. 2019;12(3):887-922.

[7] Lian Z, Lu Y, Wang C, et al. Single-atom Ru implanted on Co₃O₄ nanosheets as efficient dual-catalyst for Li-CO₂ batteries. Adv Sci. 2021;8:2102550.

[8] Chen B, Wang D, Zhang B, et al. Engineering the active sites of graphene catalyst: from CO₂ activation to activate Li-CO₂ batteries. ACS Nano. 2021;15(6):9841-9850.

[9] Guo C, Zhang F, Han X, et al. Intrinsic descriptor guided Noble metal cathode design for Li-CO₂ battery. Adv Mater. 2023;35(33):2302325.

[10] Mahne N, Renfrew SE, McCloskey BD, Freunberger SA. Electrochemical oxidation of lithium carbonate generates singlet oxygen. Angew Chem Int Ed. 2018;57(19):5529-5533.

[11] Feng H, Jia M, Lin Y, et al. Unveiling the reaction mechanism and ¹O₂ suppression effect of CO₂ in Li-CO₂/O₂ battery through the reacquaintance of discharge products. Energy Storage Mater. 2023;61:102886.

[12] Ma D, Hu B, Wu W, et al. Highly active nanostructured CoS₂/CoS heterojunction electrocatalysts for aqueous polysulfide/iodide redox flow batteries. Nat Commun. 2019;10(1):3367.

[13] Park HL, White WB. Raman spectra of FeS and β-CoS. Phys Status Solidi B. 1987;144(1):K69-K71.

[14] Weil JA, Bolton JR. Electron Paramagnetic Resonance: Elementary Theory and Practical Applications. Wiley-Interscience; 2007.

[15] Pfau A, Schierbaum KD. The electronic structure of stoichiometric and reduced CeO₂ surfaces: an XPS, UPS and HREELS study. Surf Sci. 1994;321(1-2):71-80.

[16] Wang X, Zhang Y, Si H, et al. Single-atom vacancy defect to trigger high-efficiency hydrogen evolution of MoS₂. J Am Chem Soc. 2020;142(9):4298-4308.

[17] Zhao Y, Jia X, Chen G, et al. Ultrafine NiO nanosheets stabilized by TiO₂ from monolayer NiTi-LDH precursors: an active water oxidation electrocatalyst. J Am Chem Soc. 2016;138(20):6517-6524.

[18] Yan H, Wang WW, Wu TR, et al. Morphology-dictated mechanism of efficient reaction sites for Li₂O₂ decomposition. J Am Chem Soc. 2023;145(22):11959-11968.

[19] Zhang Y, Zhang S, Li H, et al. Tunable oxygen vacancies of cobalt oxides in lithium–oxygen batteries: morphology control of discharge product. Nano Lett. 2023;23(19):9119-9125.

[20] Zhang Y, Zhang S, Ma J, Chen X, Nan C, Chen C. Single-atom-mediated spinel octahedral structures for elevated performances of Li-oxygen batteries. Angew Chem Int Ed. 2023;62(15):e202218926.

[21] Hammer B, Norskov JK. Why gold is the noblest of all the metals. Nature. 1995;376(6537):238-240.

[22] Nørskov JK, Bligaard T, Rossmeisl J, Christensen CH. Towards the computational design of solid catalysts. Nat Chem. 2009;1(1):37-46.

[23] Nørskov JK, Rossmeisl J, Logadottir A, et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J Phys Chem B. 2004;108(46):17886-17892.

[24] Shi Y, Wei B, Legut D, du S, Francisco JS, Zhang R. Highly stable single-atom modified MXenes as cathode-active bifunctional catalysts in Li–CO₂ battery. Adv Funct Mater. 2022;32(48):2210218.

[25] Chi L-P, Niu ZZ, Zhang XL, et al. Stabilizing indium sulfide for CO₂ electroreduction to formate at high rate by zinc incorporation. Nat Commun. 2021;12(1):5835.

[26] Dou T, He J, Diao S, et al. Dynamic reconstructuring of CuS/SnO₂-S for promoting CO₂ electroreduction to formate. J Energy Chem. 2023;82:497-506.

[27] Wu T, Sun Y, Ren X, et al. Reconstruction of thiospinel to active sites and spin channels for water oxidation. Adv Mater. 2023;35(2):2207041.

[28] Liu J-C, Ma XL, Li Y, Wang YG, Xiao H, Li J. Heterogeneous Fe₃ single-cluster catalyst for ammonia synthesis via an associative mechanism. Nat Commun. 2018;9(1):1610.

[29] Zhang F, Qin N, Li Y, et al. Phytate lithium as a multifunctional additive stabilizes LiCoO₂ to 4.6 V. Energy Environ Sci. 2023;16(10):4345-4355.

RIGHTS & PERMISSIONS

2024 2024 The Authors. EcoMat published by The Hong Kong Polytechnic University and John Wiley & Sons Australia, Ltd.