Physical Chemistry Research

Understanding the Decomposition Mechanism of Li2O2 in the Cathode of Li-O2 Battery with First Principles Molecular Dynamics

Document Type : Regular Article

Authors

Md. Khorshed Alam 1
Shahariar Emon 1
Hiromitsu Takaba 2

1 Department of Physics, University of Barishal, Kornokathi, Barishal-8200, Bangladesh

2 Department of Environmental Chemistry and Chemical Engineering, School of Advanced Engineering, Kogakuin University, 2665-1 Nakano Hachioji, Tokyo 192-0015, Japan

https://doi.org/10.22036/pcr.2025.512159.2655
Abstract
First-principles molecular dynamics (FPMD) regarding electron removal was used to investigate the decomposition of lithium peroxide (Li2O2) as a model of the cathode reaction in a lithium–air (Li–O2) battery. The decomposition of Li2O2 was demonstrated in a vacuum and the Li2O2 cluster at the surface of the carbon cathode as a function of the number of electrons that was removed from the system. Further, the Li2O2 cluster was decomposed into Li+ and LiO2, after which it almost formed Li+ and molecular oxygen (O2). The formation of O2 after delithiation was confirmed from the measured bond length, frequency, and atomic charge analysis. The estimated voltage that was required for the decomposition reaction was calculated from the free energy changes (~4.0 V); it agreed well with the experimental value. Moreover, the carbon layer increased the voltage, indicating that the interaction of Li2O2 with the cathode surface also contributed to the charging voltage.

Graphical Abstract

Understanding the Decomposition Mechanism of Li2O2 in the Cathode of Li-O2 Battery with First Principles Molecular Dynamics

Keywords

Lithium-air battery
Charging mechanism
Lithium peroxide
Decomposition process

Subjects

[1]  Abraham, K. M.; Jiang, Z., A Polymer Electrolyte‐Based Rechargeable Lithium/Oxygen Battery. J. Electrochem. Soc. 1996, 143, 1, DOI: 10.1149/1.1836378.
[2]  Read, J., Characterization of the Lithium/Oxygen Organic Electrolyte Battery. J. Electrochem. Soc. 2002, 149, A1190, DOI: 10.1149/1.1498256.
[3]  Girishkumar, G.; McCloskey, B.; Luntz, A. C.; Swanson, S.; Wilcke, W., Lithium-Air Battery: Promise and Challenges. J. Phys. Chem. Lett. 2010, 1, 2193-2203, DOI: 10.1021/jz1005384.
[4]  Christensen, J.; Albertus, P.; Sanchez-Carrera, R. S.; Lohmann, T.; Kozinsky, B.; Liedtke, R.; Ahmed, J.; Kojic, A., A Critical Review of Li/Air Batteries. J. Electrochem. Soc. 2011, 159, R1–R30, DOI: 10.1149/2.086202jes.
[5]  McCloskey, B. D.; Bethune, D. S.; Shelby, R. M.; Girishkumar, G.; Luntz, A. C., Solvents’ Critical Role in Nonaqueous Lithium-Oxygen Battery Electrochemistry. J. Phys. Chem. Lett. 2011, 2, 1161-1166, DOI: 10.1021/ jz200352v.
[6]  Peng, Z.; Freunberger, S. A.; Chen, Y.; Bruce, P. G., A Reversible and Higher-Rate Li-O2 Battery. Science 2012, 337, 563-566, DOI: 10.1126/science.1223985.
[7]  Zhang, Z.; Lu, J.; Assary, R. S.; Du, P.; Wang, H. -H.; Sun, Y. -K.; Qin, Y.; Lau, K. C.; Greeley, J.; Redfern, P. C.; et al. Increased Stability Toward Oxygen Reduction Products for Lithium-Air Batteries with Oligoether-Functionalized Silane Electrolytes. J. Phys. Chem. C 2011, 115, 25535-25542, DOI: 10.1021/ jp2087412.
[8]  Ogasawara, T.; Débart, A.; Holzapfel, M.; Novák, P.; Bruce, P. G., Rechargeable Li2O2 Electrode for Lithium Batteries. J. Am. Chem. Soc. 2006, 128, 1390-1393, DOI: 10.1021/ja056811q.
[9]  Mizuno, F.; Nakanishi, S.; Kotani, Y.; Yokoishi, S.; Iba, H., Rechargeable Li-Air Batteries with Carbonate-Based Liquid Electrolytes. Electrochemistry 2010, 78, 403-405, DOI: 10.5796/electrochemistry.78.403.
[10] Black, R.; Adams, B.; Nazar, L. F., Non-Aqueous and Hybrid Li-O2 Batteries. Advanced Energy Materials 2012, 2, 801-815, DOI: 10.1002/aenm.201200001.
[11] Lu, Y. -C.; Kwabi, D. G.; Yao, K. P. C.; Harding, J. R.; Zhou, J.; Zuin, L.; Shao-Horn, Y., The Discharge Rate Capability of Rechargeable Li–O2 Batteries. Energy Environ. Sci. 2011, 4, 2999-3007, DOI: 10.1039/ C1EE01500A.
[12] Harding, J.R.; Lu, Y.-C.; Tsukada, Y.; Shao-Horn, Y. Evidence of Catalyzed Oxidation of Li2O2 for Rechargeable Li–Air Battery Applications. Phys. Chem. Chem. Phys. 2012, 14, 10540-10546, DOI: 10.1039/ C2CP41761H.
[13] Laino, T.; Curioni, A., A New Piece in the Puzzle of Lithium/Air Batteries: Computational Study on the Chemical Stability of Propylene Carbonate in the Presence of Lithium Peroxide. Chemistry – A European Journal 2012, 18, 3510-3520, DOI: 10.1002/ chem.201103057.
[14]  McCloskey, B. D.; Speidel, A.; Scheffler, R.; Miller, D. C.; Viswanathan, V.; Hummelshøj, J. S.; Nørskov, J. K.; Luntz, A. C., Twin Problems of Interfacial Carbonate Formation in Nonaqueous Li–O2 Batteries. J. Phys. Chem. Lett. 2012, 3, 997-1001, DOI: 10.1021/ jz300243r.
[15] Oswald, S.; Mikhailova, D.; Scheiba, F.; Reichel, P.; Fiedler, A.; Ehrenberg, H. XPS Investigations of Electrolyte/Electrode Interactions for Various Li-Ion Battery Materials. Anal Bioanal Chem 2011, 400, 691-696, DOI: 10.1007/s00216-010-4646-z.
[16] Chalasani, D.; Lucht, B. L., Reactivity of Electrolytes for Lithium-Oxygen Batteries with Li2O2. ECS Electrochem. Lett. 2012, 1, A38, DOI: 10.1149/ 2.010202eel.
[17] Younesi, R.; Hahlin, M.; Björefors, F.; Johansson, P.; Edström, K., Li–O2 Battery Degradation by Lithium Peroxide (Li2O2): A Model Study. Chem. Mater. 2013, 25, 77-84, DOI: 10.1021/cm303226g.
[18] Hummelshøj, J. S.; Luntz, A. C.; Nørskov, J. K., Theoretical Evidence for Low Kinetic Overpotentials in Li-O2 Electrochemistry. The Journal of Chemical Physics 2013, 138, 034703, DOI: 10.1063/1.4773242.
[19] Jung, H. -G.; Hassoun, J.; Park, J. -B.; Sun, Y. -K.; Scrosati, B., An Improved High-Performance Lithium–Air Battery. Nature Chem. 2012, 4, 579-585, DOI: 10.1038/nchem.1376.
[20] Oh, S. H.; Nazar, L. F., Oxide Catalysts for Rechargeable High-Capacity Li–O2 Batteries. Advanced Energy Materials 2012, 2, 903-910, DOI: 10.1002/ aenm.201200018.
[21] Yang, J.; Zhai, D.; Wang, H. -H.; Lau, K. C.; Schlueter, J. A.; Du, P.; Myers, D. J.; Sun, Y. -K.; Curtiss, L. A.; Amine, K., Evidence for Lithium Superoxide-like Species in the Discharge Product of a Li–O2 Battery. Phys. Chem. Chem. Phys. 2013, 15, 3764-3771, DOI: 10.1039/C3CP00069A.
[22] Younesi, R.; Hahlin, M.; Treskow, M.; Scheers, J.; Johansson, P.; Edström, K., Ether Based Electrolyte, LiB(CN)4 Salt and Binder Degradation in the Li–O2 Battery Studied by Hard X-Ray Photoelectron Spectroscopy (HAXPES). J. Phys. Chem. C 2012, 116, 18597-18604, DOI: 10.1021/jp303691m.
[23] Freunberger, S. A.; Chen, Y.; Peng, Z.; Griffin, J. M.; Hardwick, L. J.; Bardé, F.; Novák, P.; Bruce, P. G., Reactions in the Rechargeable Lithium–O2 Battery with Alkyl Carbonate Electrolytes. J. Am. Chem. Soc. 2011, 133, 8040-8047, DOI: 10.1021/ja2021747.
[24] Younesi,  R.;  Hahlin,  M.; Roberts,  M.; Edström, K., The SEI Layer Formed on Lithium Metal in the Presence of Oxygen: A Seldom Considered Component in  the Development of the Li–O2 Battery. Journal of Power Sources 2013, 225, 40-45, DOI: 10.1016/ j.jpowsour.2012.10.011.
[25] Assary, R. S.; Lu, J.; Du, P.; Luo, X.; Zhang, X.; Ren, Y.; Curtiss, L. A.; Amine, K., The Effect of Oxygen Crossover on the Anode of a Li–O2 Battery Using an Ether‐Based Solvent: Insights from Experimental and Computational Studies. ChemSusChem 2013, 6, 51-55, DOI: 10.1002/cssc.201200810.
[26] Oh, S. H.; Black, R.; Pomerantseva, E.; Lee, J. -H.; Nazar, L. F., Synthesis of a Metallic Mesoporous Pyrochlore as a Catalyst for Lithium–O2 Batteries. Nature Chem. 2012, 4, 1004-1010, DOI: 10.1038/ nchem.1499.
[27] Elghazali, A.; Aboulouard, A.; Zouitina, S.; Atlas, S.; Idrissi, M.; Tounsi, A., First-Principles Study on Optoelectronic and Photovoltaic Properties in a P3HT/PCBM Complex. PCR 2023, 11, DOI: 10.22036/ pcr.2022.339408.2087.
[28] Saidi, F.; Dergal, M.; Dendane, A.; Ameur, N., First-Principles Investigation of Structural Stability, Electronic and Optical Properties of V Y-Doped and (V Y)-Codoped Monoclinic ZrO2. PCR 2024, 12, DOI: 10.22036/pcr.2023.416669.2419.
[29] Delley, B., An All‐electron Numerical Method for Solving the Local Density Functional for Polyatomic Molecules. The Journal of Chemical Physics 1990, 92, 508-517, DOI: 10.1063/1.458452.
[30] Delley, B., Fast Calculation of Electrostatics in Crystals and Large Molecules. J. Phys. Chem. 1996, 100, 6107-6110, DOI: 10.1021/jp952713n.
[31] Delley, B., From Molecules to Solids with the DMol3 Approach. The Journal of Chemical Physics 2000, 113, 7756-7764, DOI: 10.1063/1.1316015.
[32] Perdew, J. P.; Burke, K.; Ernzerhof, M., Generalized Gradient Approximation Made Simple. Phys. Rev.Lett. 1996, 77, 3865-3868, DOI: 10.1103/ PhysRevLett.77.3865.
[33] Mo, Y.; Ong, S. P.; Ceder, G., First-Principles Study of the Oxygen Evolution Reaction of Lithium Peroxide in the Lithium-Air Battery. Phys. Rev. B 2011, 84, 205446, DOI: 10.1103/PhysRevB.84.205446.
[34] Braga, C.; Travis, K. P., A Configurational Temperature Nosé-Hoover Thermostat. J. Chem. Phys. 2005, 123, 134101, DOI: 10.1063/1.2013227.
[35] Cota, L. G.; De La Mora, P., On the Structure of Lithium Peroxide, Li2O2. Acta Crystallographica Section B 2005, 61, 133-136, DOI: 10.1107/S0108768105003629.
[36] BIOVIA, Dassault Systemes, San Diego, USA Material Studio Package.
[37] Hou, B.; Lei, X.; Gan, Z.; Zhong, S.; Liu, G.; Ouyang, C., Structural and Electronic Properties of Small Lithium Peroxide Clusters in View of the Charge Process in Li–O2 Batteries. Phys. Chem. Chem. Phys. 2019, 21, 19935-19943, DOI: 10.1039/C9CP03785C.
[38] Lau, K. C.; Assary, R. S.; Redfern, P.; Greeley, J.; Curtiss, L. A., Electronic Structure of Lithium Peroxide Clusters and Relevance to Lithium-Air Batteries. J. Phys. Chem. C 2012, 116, 23890-23896, DOI: 10.1021/ jp306024f.
[39] Ling, C.; Zhang, R.; Takechi, K.; Mizuno, F., Intrinsic Barrier to Electrochemically Decompose Li2CO3 and LiOH. J. Phys. Chem. C 2014, 118, 26591-26598, DOI: 10.1021/jp5093306.
[40] Laoire, C. O.; Mukerjee, S.; Abraham, K. M.; Plichta, E. J.; Hendrickson, M. A., Elucidating the Mechanism of Oxygen Reduction for Lithium-Air Battery Applications. J. Phys. Chem. C 2009, 113, 20127-20134, DOI: 10.1021/jp908090s.
[41] Lu, Y. -C.; Gasteiger, H. A.; Crumlin, E.; McGuire, R.; Shao-Horn, Y., Electrocatalytic Activity Studies of Select Metal Surfaces and Implications in Li-Air Batteries. J. Electrochem. Soc. 2010, 157, A1016, DOI: 10.1149/1.3462981.
[42] Débart, A.; Bao, J.; Armstrong, G.; Bruce, P. G., An O2 Cathode for Rechargeable Lithium Batteries: The Effect of a Catalyst. Journal of Power Sources 2007, 174, 1177-1182, DOI: 10.1016/j.jpowsour.2007.06.180.
[43] Thapa, A. K.; Saimen, K.; Ishihara, T., Pd/MnO[Sub 2] Air Electrode Catalyst for Rechargeable Lithium/Air Battery. Electrochem. Solid-State Lett. 2010, 13, A165, DOI: 10.1149/1.3481762.
[43] Lu, Y. -C.; Gasteiger, H. A.; Parent, M. C.; Chiloyan, V.; Shao-Horn, Y., The Influence of Catalysts on Discharge and  Charge Voltages of Rechargeable Li–Oxygen Batteries. Electrochem. Solid-State Lett. 2010, 13, A69, DOI: 10.1149/1.3363047.
Physical Chemistry Research
Volume 13, Issue 4
Autumn 2025
Pages 677-686

  • Receive Date 14 March 2025
  • Revise Date 05 July 2025
  • Accept Date 29 July 2025