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First-Principles Simulations for the Surface Evolution and Mn Dissolution in the Fully Delithiated Spinel LiMn2O4
Xiaorui Sun1,2, Ruijuan Xiao1,2, Xiqian Yu1,2
1Beijing Advanced Innovation Center for Materials Genome Engineering, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
Investigating manganese dissolution in lithium-ion batteries reveals that surface oxygen loss and electrolyte decomposition drive cathode material degradation, impacting battery life and performance.
Area of Science:
- Materials Science
- Electrochemistry
- Computational Chemistry
Background:
- Interfacial stability is crucial for high-energy lithium-ion batteries.
- Manganese dissolution in LiMn2O4 causes capacity fade, making it a key research case.
Purpose of the Study:
- To elucidate the mechanisms of manganese dissolution at the cathode-electrolyte interface.
- To understand the role of ethylene carbonate decomposition in this process.
Main Methods:
- Ab initio molecular dynamics (AIMD) simulations were employed.
- The interface between ethylene carbonate and the LiMn2O4 (110) surface was modeled.
Main Results:
- Surface oxygen loss initiates manganese atom migration and reduction.
- Ethylene carbonate decomposition, triggered by electron transfer, exacerbates manganese dissolution.
- Oxygen loss and ethylene carbonate decomposition compete for electron transfer.
Conclusions:
- A detailed step-by-step mechanism for manganese dissolution and interfacial evolution in LiMn2O4 was established.
- This study offers insights into transition-metal dissolution relevant to other battery chemistries.
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