Investigation on the dissolution of Mn ions from LiMn<sub>2</sub>O<sub>4</sub> cathode in the application of lithium ion batteries: First principle molecular orbital method

Kim, Yongseon; Lim, Jin Ho; Kang, Shinhoo

doi:10.1002/qua.24314

Cited by 36 publications

(29 citation statements)

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“…The Mn dissolution is also affected by the electronic property of Mn, as previous studies have reported. [ 23,57–60 ] The electronic orbital configuration for oxidation of Mn 3+ is depicted in Figure 5A. The electronic configuration of Mn 3+ has three electrons in the t 2g orbital and one electron in the e g orbital.…”

Section: Resultsmentioning

confidence: 99%

“…From the summation of all COOP values under the Fermi energy, which was an indicator of the covalent character of a chemical bonding. [ 23 ]…”

Section: Methodsmentioning

confidence: 99%

“…It has been reported that the covalent nature of a Mn–O bond has a direct impact on metal‐ion dissolution. [ 22,23 ] The Mn–O bond is distorted, due to the dissolution of the Mn 2+ ions, resulting in a change in the Mn charge densities. Typically, Mn 4+ with a t 2g electron configuration and MnO 2 are highly stable.…”

Section: Introductionmentioning

confidence: 99%

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Discovery of an Unexpected Metal Dissolution of Thin‐Coated Cathode Particles and Its Theoretical Explanation

Pham

Gao

et al. 2020

Advcd Theory and Sims

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The degree of metal dissolution of cathode materials is a critical parameter in determining the performance of lithium-ion batteries (LIBs). Ultra-thin coated cathode particles, fabricated via atomic layer deposition (ALD), exhibit superior battery performance over that of bare particles. Therefore, it is generally believed that a coating layer protects the particles from metal dissolution of active materials, which is a critical cathode degradation mechanism. However, it is observed that ultra-thin CeO 2 coating intensified the Mn dissolution of LiMn 2 O 4 (LMO) during cycling of LIBs, whereas ultra-thin Al 2 O 3 coating tended to inhibit Mn dissolution. A detailed density functional theory (DFT) study is carried out to explain these experimental observations by analyzing interaction of Mn atoms with neighboring electrode atoms in terms of energetic and structural aspect. All atomic and electronic analyses are consistent with the experimental observations. Several common materials are investigated as possible ALD coatings for LIBs to provide general insight, and it is found that Mn dissolution can be suppressed or accelerated depending on the material selection. This is the first report finding that depending on the coating material, metal dissolution can be accelerated, providing new insights into the impact of ALD coating materials on metal dissolution in cathode materials. potential, superior capacity, a long life cycle, and a sufficiently broad range of working temperatures. Although metal oxide cathodes satisfy the criteria, they suffer from an inevitable metal dissolution degradation process. In the dissolution degradation process, transition metal ions dissolve from cathode active materials and can deposit onto the anode, causing severe cell aging and irreversible side reactions that reduce performance. [1,2] For high performance cathode materials such as LiNi x Mn y Co z O 2 (NMC, x + y + z = 1), LiNi 0.5 Mn 1.5 O 4 (LNMO), and LiMn 2 O 4 (LMO), metal dissolution (Ni, Co, Mn, etc.) is severe, and, furthermore, it was found that in such cathode materials, which are composed of two or more transition metals, there is no preferential dissolution among the constituent metals. [3] To study the metal dissolution phenomena, manganese is an excellent candidate for intensive study of the fundamental interfacial processes and side reactions at cathode surfaces because of its low toxicity, low cost, and the high natural abundance of Mn, [4][5][6][7][8][9][10][11][12] which allows it to be used in several promising cathode materials, such as NMC, LNMO, and LMO. It has been published that Mn dissolution accounts for 23% and 34% of overall capacity degradation at room temperature and at 55°C [13] in LMO, respectively. The major reason for LMO degradation, [14][15][16][17][18] as well as for other metal oxide cathode materials, [3,[19][20][21] has been identified as structural changes in the material due to phase transformations, alternation of intrinsic properties (such as electronic and ionic conductivity), dissoluti...

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Section: Resultsmentioning

confidence: 99%

“…From the summation of all COOP values under the Fermi energy, which was an indicator of the covalent character of a chemical bonding. [ 23 ]…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Discovery of an Unexpected Metal Dissolution of Thin‐Coated Cathode Particles and Its Theoretical Explanation

Pham

Gao

et al. 2020

Advcd Theory and Sims

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“…This method does not use the pseudopotential approximation. All the atomic orbitals of the model cluster are included in the calculation, which can provide reliable information on the molecular orbitals and electron distributions …”

Section: Methodsmentioning

confidence: 99%

Investigation of the change in the electronic properties of FeF₃by the introduction of oxygen using a molecular orbital method

Kim

Choi

Kim

2013

Int. J. Quantum Chem.

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FeF3 has attracted interest as a conversion‐reaction‐based positive electrode material in applications to lithium ion batteries. However, slow reaction kinetics is a major drawback due to its poor electrical conductivity. The electronic features of FeF3 were examined using the DV‐Xα molecular orbital method. This article reports the effects of oxygen doping on the bonding characteristics and electrical conductivity. An analysis of the bond overlap population and spatial distribution of electrons showed that the FeO bond has a more covalent nature than the FeF bond. New energy levels were generated in the original band gap region through an interaction between the Fe3d and O2p orbitals with the introduction of oxygen. The electrical conductivity of FeF3 is expected to be increased by the partial substitution of oxygen for fluorine due to the higher covalent character and the formation of new energy levels. © 2013 Wiley Periodicals, Inc.

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“…It is reported that substitution of Mn ions with other metals such as Mg, Al, Cr, Co, Ni, Zn, Mg, Ga slows dissolution of Mn into the electrolyte [4]. Partial replacing Mn, could increase the average valence of Mn in LiMn 2 O 4 (decreasing the Mn 3+ in LiMn 2 O 4 ), and could supress the Jahn-Teller eect [5]. The present work is focused on the understanding of bication eect of (Cr 3+ and V 5+ ) substituted on LiMn 2 O 4 cathode in addressing the hampering issues that are concerned with the unacceptable capacity fade and the poor cycle life behavior of spinel cathode.…”

Section: Introductionmentioning

confidence: 99%

Cr and V Substitution in the LiMn₂O₄Spinel Positive Electrode Li-Ion Batteries

Akbulut

Çetinkaya²,

Guler³

et al. 2015

Acta Phys. Pol. A

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In this study, LiCr0.2V0.4Mn1.4O4 cathode active electrode materials were produced via a facile sol-gel method at 800• C. The surfaces of the LiCr0.2V0.4Mn1.4O4 cathode active electrode materials were then coated with Cu in order to increase the conductivity and suppress the manganese ion dissolution into the electrolyte. The structure and electrochemical properties of the obtained Cr and V substituted LiMn2O4 powders were investigated by X-ray diraction (XRD), scanning electron microscopy (SEM), galvanostatic charge-discharge test and electrochemical impedance spectroscopy (EIS). The improvement in the cycling performances attributed to stabilization of spinel structure by bication ion substation and Cu coating on the spinel particles. EIS analysis conrmed that bication doping and conductive Cu coating contributed stability of the spinel electrodes and provided stable electrolyte/electrode interface due to the suppression of electrolyte decomposition

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Investigation on the dissolution of Mn ions from LiMn₂O₄ cathode in the application of lithium ion batteries: First principle molecular orbital method

Cited by 36 publications

References 36 publications

Discovery of an Unexpected Metal Dissolution of Thin‐Coated Cathode Particles and Its Theoretical Explanation

Discovery of an Unexpected Metal Dissolution of Thin‐Coated Cathode Particles and Its Theoretical Explanation

Investigation of the change in the electronic properties of FeF₃by the introduction of oxygen using a molecular orbital method

Cr and V Substitution in the LiMn₂O₄Spinel Positive Electrode Li-Ion Batteries

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Investigation on the dissolution of Mn ions from LiMn2O4 cathode in the application of lithium ion batteries: First principle molecular orbital method

Cited by 36 publications

References 36 publications

Discovery of an Unexpected Metal Dissolution of Thin‐Coated Cathode Particles and Its Theoretical Explanation

Discovery of an Unexpected Metal Dissolution of Thin‐Coated Cathode Particles and Its Theoretical Explanation

Investigation of the change in the electronic properties of FeF3by the introduction of oxygen using a molecular orbital method

Cr and V Substitution in the LiMn2O4Spinel Positive Electrode Li-Ion Batteries

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Product

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Investigation on the dissolution of Mn ions from LiMn₂O₄ cathode in the application of lithium ion batteries: First principle molecular orbital method

Investigation of the change in the electronic properties of FeF₃by the introduction of oxygen using a molecular orbital method

Cr and V Substitution in the LiMn₂O₄Spinel Positive Electrode Li-Ion Batteries