Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn2O4 Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Zhuang, G.; Sun, Xiaorui; Li, Qing-Hao; Wang, Xuelong; Zhang, Jie-Nan; Yang, Wanli; Yu, Xiqian; Xiao, Ruijuan; Li, Hong

doi:10.1021/acs.jpclett.0c00936

Cited by 75 publications

(60 citation statements)

References 49 publications

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“…On the other hand, it is more challenging to understand the complicated interactions at the solid–liquid interface during electrochemical cycling, especially the formation and dynamic evolution of CEIs, decomposition and oxidation of organic electrolytes, and surface diffusion, solvation, and dissolution of Mn and other TM species. It again requires synergetic efforts with various ex situ and in situ characterization tools (e.g., time‐of‐flight secondary‐ion mass spectroscopy, [ 60 ] ultraviolet–visible spectroscopy [ 61 ] ) and advanced simulation techniques (e.g., ab initio molecular dynamics simulations [ 61,62 ] ) to capture and understand the underlying thermodynamics and dynamics, which could help to design stable artificial CEIs, novel electrolytes, and additives to fully solve the TM dissolution problem. Such mechanistic understandings hold the key for the future development of spinel cathodes.…”

Section: Degradation Mechanisms Of Spinel Cathodesmentioning

confidence: 99%

Lithium Manganese Spinel Cathodes for Lithium‐Ion Batteries

Huang

Dong

et al. 2020

Advanced Energy Materials

255

169

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Spinel LiMn2O4, whose electrochemical activity was first reported by Prof. John B. Goodenough's group at Oxford in 1983, is an important cathode material for lithium‐ion batteries that has attracted continuous academic and industrial interest. It is cheap and environmentally friendly, and has excellent rate performance with 3D Li+ diffusion channels. However, it suffers from severe degradation, especially under extreme voltages and during high‐temperature operation. Here, the current understanding and future trends of the spinel cathode and its derivatives with cubic lattice symmetry (LiNi0.5Mn1.5O4 that shows high‐voltage stability, and Li‐rich spinels that show reversible hybrid anion‐ and cation‐redox activities) are discussed. Special attention is given to the degradation mechanisms and further development of spinel cathodes, as well as concepts of utilizing the cubic spinel structure to stabilize high‐capacity layered cathodes and as robust framework for high‐rate electrodes. “Good spinel” surface phases like LiNi0.5Mn1.5O4 are distinguished from “bad spinel” surface phases like Mn3O4.

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Section: Degradation Mechanisms Of Spinel Cathodesmentioning

confidence: 99%

Lithium Manganese Spinel Cathodes for Lithium‐Ion Batteries

Huang

Dong

et al. 2020

Advanced Energy Materials

255

169

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“…38−40 And in the previous work, we proposed that the dissolution of Mn is the result of interface evolution. 41 In brief, the core factors of the interface evolution between the LMO cathode and the electrolyte have been covered in the existing work.…”

Section: ■ Introductionmentioning

confidence: 99%

First-Principles Simulations for the Surface Evolution and Mn Dissolution in the Fully Delithiated Spinel LiMn₂O₄

Sun

Xiao

et al. 2021

Langmuir

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The interfacial stability between the cathode and electrolyte is an essential issue in the development of high-energy-density and long-life lithium-ion batteries. The deterioration of capacity dominated by Mn dissolution makes LiMn2O4 a representative case for studying the evolution of interfaces. Here, we use the ab initio molecular dynamics (AIMD) method to simulate the interface reaction between the ethylene carbonate (EC) molecules and the (110) surface of completely delithiated LiMn2O4 where most severe Mn dissolution is observed in the experiment. It is found that the intrinsic oxygen loss on the surface will drive the initial migration of surface Mn atoms to the electrolyte while reducing them. The EC molecules will decompose after transferring electrons to the surface Mn atoms, and its decomposition products further promote the Mn dissolution. In addition, oxygen loss and EC decomposition are in a competitive relationship when transferring electrons to the surface Mn atoms. This work provides a complete picture of the step-by-step dissolution of Mn atoms along with the interfacial evolution in the spinel LiMn2O4 system and also provides a scope for the study of transition-metal dissolution in other cathode materials and electrolytes.

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“…The material shows a theoretical capacity of 148 mAh g -1 and a discharge potential of 4 V [223]. But LiMn 2 O 4 cathode has a significant issue of Mn dissolution [224]. The insertion of Ni into the spinel structure of LiMn 2 O 4 forming LiNi 0.5 Mn 1.5 O 4 (LNMO) leads to an increased operating voltage of 4.7 V vs. Li + /Li.…”

Section: Spinel Oxidesmentioning

confidence: 99%

A Review on High-Capacity and High-Voltage Cathodes for Next-Generation Lithium-ion Batteries

Ghosh¹,

charjee²,

Bhowmik³

et al. 2021

JEPT

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lithium-ion battery (LIB) is at the forefront of energy research. Over four decades of research and development have led electric mobility to a reality. Numerous materials capable of storing lithium reversibly, either as an anode or as a cathode, are reported on a daily basis. But very few among them, such as LiCoO2, lithium nickel manganese cobalt oxide (Li-NMC) variants (LiNi0.33Mn0.33Co0.33O2, LiNi0.5Mn0.3Co0.2O2, LiNi0.6Mn0.2Co0.2O2, and LiNi0.8Mn0.1Co0.1O2), LiNi0.8Co0.15Al0.05O2, LiFePO4, graphite, and Li4Ti5O12 are successful at commercial scale. Future energy requirements demand a push in the energy density of LIBs to meet the criteria of electric aviation, power trains, stationary grids, etc. All these applications have different needs which cannot be satisfied by a particular set of materials. Therefore, various materials need to be utilized in widespread fields of battery applications in the near future. This review discusses potential cathode materials that show a capacity of ≥ 250 mAh g-1 (Li-rich oxides, conversion materials, etc.) or average voltage of ≥ 4 V vs. Li+/Li (polyanionic materials, spinel oxides, etc.). Failure mechanisms, challenges, and way-outs to overcome all the issues are put forward to determine commercial viability.

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Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Cited by 75 publications

References 49 publications

Lithium Manganese Spinel Cathodes for Lithium‐Ion Batteries

Lithium Manganese Spinel Cathodes for Lithium‐Ion Batteries

First-Principles Simulations for the Surface Evolution and Mn Dissolution in the Fully Delithiated Spinel LiMn₂O₄

A Review on High-Capacity and High-Voltage Cathodes for Next-Generation Lithium-ion Batteries

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Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn2O4 Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

Cited by 75 publications

References 49 publications

Lithium Manganese Spinel Cathodes for Lithium‐Ion Batteries

Lithium Manganese Spinel Cathodes for Lithium‐Ion Batteries

First-Principles Simulations for the Surface Evolution and Mn Dissolution in the Fully Delithiated Spinel LiMn2O4

A Review on High-Capacity and High-Voltage Cathodes for Next-Generation Lithium-ion Batteries

Contact Info

Product

Resources

About

Mn Ion Dissolution Mechanism for Lithium-Ion Battery with LiMn₂O₄ Cathode: In Situ Ultraviolet–Visible Spectroscopy and Ab Initio Molecular Dynamics Simulations

First-Principles Simulations for the Surface Evolution and Mn Dissolution in the Fully Delithiated Spinel LiMn₂O₄