橄榄石型材料离子-电子耦合转移过程中的分子轨道理论描述和计算研究

doi:10.12461/PKU.DXHX202404054

Abstract

Abstract: The electronic coupling matrix elements play a crucial role in the ion-coupled electron transfer processes in olivine-type phosphate cathode materials. By combining Density Functional Theory (DFT) calculations with molecular orbital theory, this study reveals a positive correlation between the magnitude of the electronic coupling matrix elements and the electron density distribution near the Fermi level of the transition metal centers in olivine-type cathode materials. Furthermore, the study establishes a quantitative relationship between the electronic structure of the metal centers and the Li⁺ diffusion coefficients. These findings provide new theoretical insights for the development of high-performance lithium-ion battery cathode materials by optimizing the electronic coupling in host materials.

Key words: Molecular orbital theory, Electronic coupling matrix elements, Ion-coupled electron transfer, DFT calculation

Yu Gao, Xiaoxiao Wang, Yingying Li, Shengli Chen. Molecular Orbital Theory Description and Computational Study of Ion-Coupled Electron Transfer in Olivine-Type Materials[J].University Chemistry, 2024, 39(12): 369-377.

References

[1] Takahashi, M.; Ohtsuka, H.; Akuto, K.; Sakurai, Y. J. Electrochem. Soc. 2005, 152, A899.
[2] Lepage, D.; Michot, C.; Liang, G.; Gauthier, M.; Schougaard, S. B. Angew. Chem. Int. Ed. 2011, 50, 6884.
[3] Yang, X.; Tu, J.; Lei, M.; Zuo, Z.; Wu, B.; Zhou, H. Electrochimi. Acta 2016, 193, 206.
[4] Chandrasekaran, R. J. Power Sources 2014, 271, 622.
[5] Padhi, A.; Nanjundaswamy, K. S.; Goodenough, J. B. J. Electrochem. Soc. 1997, 144, 1188.
[6] Chung, S. Y.; Blocking, J. T.; Chiang, Y. M. Nat. Mater. 2002, 1, 123.
[7] Hu, J.; Huang, W.; Yang, L.; Pan, F. Nanoscale 2020, 12 (28), 15036.
[8] Bi, Z.; Zhang, X.; He, W.; Min, D.; Zhang, W. RSC Adv. 2013, 3 (43), 19744.
[9] Eftekhari, A. J. Power Sources 2017, 343, 395.
[10] Kang, B.; Ceder, G. Nature 2009, 458, 190.
[11] Lu, X. K.; Lagnoni, M.; Bertei, A.; Das, A.; Owen, R. E.; Li, Q.; O’Regan, K.; Wade, A.; Finegan, D. P.; Kendrick, E.; et al. Nat. Commun. 2023, 14 (1), 5127.
[12] Franger, S.; Le Cras, F.; Bourbon, C.; Rouault, H. Electrochem. Solid-State Lett. 2002, 5, A231.
[13] Prosini, P. P.; Lisi, M.; Zane, M.; Pasquali, M. Solid State Ionics 2002, 148, 45.
[14] Amin, R.; Balaya, P.; Maier, J. Solid-State Lett. 2007, 10, A13.
[15] Wang, J.; Sun, X. Energ. Environ. Sci. 2012, 5 (1), 5163.
[16] Morgan, D.; Van der Ven, A. Solid-State Lett. 2004, 7, A30.
[17] Tao, G. H. J. Phys. Chem. C 2016, 120, 6938.
[18] Ellis, B.; Perry, L. K.; Ryan, D. H.; Nazar, L. F. J. Am. Chem. Soc. 2006, 128, 11416.
[19] Maxisch, T.; Zhou, F.; Ceder, G. Phys. Rev. B: Condens. Matter Mater. Phys. 2006, 73, 104301.
[20] Gao, Y.; Huang, J.; Liu, Y. W.; Chen, S. L. Chem. Sci. 2022, 13 (1), 257.
[21] 冯晓晗, 孙杰, 何健豪, 魏义华, 周成冈, 孙睿敏. 储能科学与技术, 2022, 11 (2), 467.
[22] Marcus, R. A. Annu. rev. phys. chem. 1964, 15 (1), 155.
[23] Burdett, J. K. Prog. Solid State Chem. 1984, 15 (3), 173.
[24] Viay, S.; Kastlunger, G.; Chan, K.; NØrskov, J. K. J. Chem. Phys. 2022, 156 (23), 231102.
[25] Dathar, G. K. P.; Sheppard, D.; Stevenson, K. J.; Henkelman, G. Chem. Mater. 2011, 23, 4032.
[26] Goodenough, J. B.; Kim, Y. Chem. Mater. 2010, 22, 587.
[27] Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. rev. lett. 1996, 77, 3865.
[28] Shang, S. L.; Wang, Y.; Mei, X. D.; Liu, Z. K. J. Mater. Chem. 2012, 22, 1142.
[29] Zhou, F.; Kang, K.; Maxisch, T.; Ceder, G.; Morgan, D. Solid State Commun. 2004, 132 (3-4), 181.
[30] Farazdel, A.; Dupuis, M.; Clementi, E.; Aviram, A. J. Am. Chem. Soc. 1990, 112 (11), 4206.
[31] Sutin, N. Acc. Chem. Res. 1982, 15, 275.
[32] Pieczonka, N. P.; Liu, Z.; Huq, A.; Kim, J. H. J. Power Sources 2013, 230, 122.

Molecular Orbital Theory Description and Computational Study of Ion-Coupled Electron Transfer in Olivine-Type Materials

PDF

Like

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Metrics

Recommended 0

[1]	Chengtian Liang, Boyuan Zheng, Ning Fang. Analysis of Coordination Chemistry Test Questions in the 38th China Chemistry Olympiad (Preliminary Round) [J]. University Chemistry, 2025, 40(8): 394-400.
[2]	Jiabo Huang, Quanxin Li, Zhongyan Cao, Li Dang, Shaofei Ni. Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations [J]. University Chemistry, 2025, 40(3): 153-159.
[3]	Ronghao Zhao, Yifan Liang, Mengyao Shi, Rongxiu Zhu, Dongju Zhang. Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment [J]. University Chemistry, 2024, 39(4): 305-313.
[4]	Qian Huang, Zhaowei Li, Jianing Zhao, Ao Yu. Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon [J]. University Chemistry, 2024, 39(3): 395-400.
[5]	Chi Zhang, Suqi Wu, An Liu, Wei Zhang, Xiao Wei. Application of Team-Based Learning Teaching Method in Inorganic Chemistry Course: the Design Case of Inorganic Chemistry Teaching in Chemistry “101 Plan” [J]. University Chemistry, 2024, 39(10): 89-95.
[6]	Zhexuan Song, Yang Hu, Xiangyu Wu, Jing Xie. Comment and Improvement on "Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations" [J]. University Chemistry, 2023, 38(9): 280-286.
[7]	Fengyi Liu, Yi Zhong, Weina Wang, Wenliang Wang. Application of Multireference ab initio Calculation in Teaching of Structure and Bonding Nature of 2nd Row Diatomic Molecules [J]. University Chemistry, 2023, 38(9): 308-312.
[8]	Rongxiu Zhu, Xiaomo Wang, Jinxin Guo, Dongju Zhang. Understanding the Effect of Solvents on the Nucleophilicity of CH₃O⁻/CH₃S⁻ Using Quantum Chemical Calculations [J]. University Chemistry, 2023, 38(2): 271-276.
[9]	Zhenzhen Xue, Jie Pan, Guoming Wang. Application of PBL Methodology in the Teaching of Hückel Molecular Orbital Theory in Structural Chemistry [J]. University Chemistry, 2023, 38(12): 274-278.
[10]	Weijia Li, Kai Liu, Yixiang Wang, Zhijun Zhang, Yiying Yang, Dongju Zhang. Exploring Stereospecificity, Regioselectivity, and Stereoselectivity in Diels-Alder Reactions: Insights from HMO Method, FMO Theory, and DFT Calculations [J]. University Chemistry, 2023, 38(11): 249-255.
[11]	Wenfeng Wang, Yaofeng Yuan. A Discussion on the Structure and Stability of Various Carbocations [J]. University Chemistry, 2023, 38(11): 267-275.
[12]	Rongxiu Zhu, Jinxin Guo, Yiying Yang, Dongju Zhang. Quantum Chemical Calculation Study of the Mechanism and Migratory Aptitude of the Baeyer-Villiger Rearrangement: Recommending a Research-Oriented Computational Chemistry Experiment [J]. University Chemistry, 2023, 38(10): 258-265.
[13]	Wenhua Xu, Anyang Li, Kefen Yue. Bonding Analysis of AB₄-Type Oxyacid Negative Ions of Main Group Elements: A Recommendation of a Research-Oriented Computational Chemistry Experiment [J]. University Chemistry, 2022, 37(2): 2108101-.
[14]	Xuexiang Ma, Chengbu Liu, Dongju Zhang. Revealing the Stereoselective Rule of Electrocyclic Reactions of Chain Conjugated Polyenes by Performing Quantum Chemical Calculations [J]. University Chemistry, 2022, 37(12): 2112089-0.
[15]	Guanghui Chen, Xinming Du, Wangqiang Lin, Li Ma, Kun Jiang. Study of Multi-Level Teaching on the Principle of Symmetry-Adapted Atomic Orbitals [J]. University Chemistry, 2022, 37(11): 2112073-0.