α-MnO2 as a cathode material for rechargeable Mg batteries

Zhang, Ruigang; Yu, Xiqian; Nam, Kyung‐Wan; Ling, Chen; Arthur, Timothy S.; Song, Wei; Knapp, Angela M.; Ehrlich, Steven N.; Yang, Xiao‐Qing; Matsui, Masaki

doi:10.1016/j.elecom.2012.07.021

Cited by 302 publications

(247 citation statements)

References 18 publications

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“…Recent studies of α-MnO 2 have also demonstrated a high initial capacity in excess of 280 mA h g −1 for Mg-ion intercalation, though significant capacity fading occurred with cycling. 40,41 Due to its large 2 × 2 tunnels, α-MnO 2 shows promise for Na-ion insertion for which we computationally evaluate the mechanisms in this work. By targeting the α-MnO 2 polymorph it may be possible to overcome existing limitations on the kinetics and complex insertion processes for Na ions.…”

Section: Introductionmentioning

confidence: 99%

Electrochemistry of Hollandite α-MnO₂: Li-Ion and Na-Ion Insertion and Li₂O Incorporation

2013

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MnO 2 is attracting considerable interest in the context of rechargeable batteries, supercapacitors, and Li−O 2 battery applications. This work investigates the electrochemical properties of hollandite α-MnO 2 using density functional theory with Hubbard U corrections (DFT+U). The favorable insertion sites for Li-ion and Na-ion insertion are determined, and we find good agreement with measured experimental voltages. By explicit calculation of the phonons we suggest multiple insertion sites are accessible in the dilute limit. Significant structural changes in α-(Li,Na) x MnO 2 during ion insertion are demonstrated by determining the low energy structures. The significant distortions to the unit cell and Mn coordination are likely to be active in causing the observed degradation of α-MnO 2 with cycling. The presence of Li 2 O in the structure reduces these distortions significantly and is the probable cause for the good experimental cycling stability of α-[0.143Li 2 O]-MnO 2 . However, the presence of Na 2 O is less effective in reducing the distortion of the Na-ion intercalated form. We also find a distinct change in the favored Li-ion insertion site, not identified in previous studies, for lithiation of α-Li x MnO 2 at x > 0.5. The migration barriers for both Li-ions and Na-ions increase from <0.3 eV in the dilute limit to >0.48 eV for α-(Li,Na) 0.75 MnO 2 . Finally, the electronic density of states in α-MnO 2 with the incorporation of Li 2 O has the character of a full metal, not a half metal as was suggested in previous work. This may be key to its good performance as a catalyst in Li−O 2 batteries.

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Section: Introductionmentioning

confidence: 99%

Electrochemistry of Hollandite α-MnO₂: Li-Ion and Na-Ion Insertion and Li₂O Incorporation

2013

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“…[29][30][31] Among them, MnO2 is perhaps the most extensively studied electrode material in many kinds of batteries. [32][33][34] Several polymorphs of MnO2 have also been investigated as possible MIB cathodes, [35][36][37][38][39] especially α-MnO2. It showed a high specific capacity of ~280 mAh g -1 in the initial discharge, but poor cyclic performance (retained ∼50 mAh g -1 after just five cycles).…”

Section: Introductionmentioning

confidence: 99%

Sponge-Like Porous Manganese(II,III) Oxide as a Highly Efficient Cathode Material for Rechargeable Magnesium Ion Batteries

et al. 2016

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Here, we are the first to report a spinel type Mn3O4 as cathode material for Mg-ion battery (MIB) with graphite foil (Gif) as current collector. High coulombic efficiency and good cyclic stability of Mn3O4 are demonstrated, and the process is enhanced by using Mn3O4 nanoparticles with a sponge-like morphology. The powder exhibits a network of interconnected mesopores with well-dispersed nanoparticles (~10 nm) and large specific surface area (102 m 2 g -1 ). This structural configuration provides easy access for electrolyte penetration which markedly enhances the utilization of electroactive material, generates high ion flux across the electrode-electrolyte interface and provides more active sites for electrochemical reactions to occur. This study can possibly open the way for exploring other similar compounds with a spinel type structure for MIB.

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“…3 ) at the fi rst discharge cycle using hexamethyldisilazide magnesium chloride (HMDS-MgCl) as electrolyte. 30 The Columbic effi ciency of the fi rst cycle exceeded 100%, possibly due to side reactions in the charge process such as Mg deposition and electrolyte decomposition. The reversible magnesiation/demagnesiation was proven by x-ray photoelectron spectroscopy (XPS) and x-ray absorption spectroscopy (XAS) of Mn states.…”

Section: Oxide Cathodesmentioning

confidence: 99%

Status and challenge of Mg battery cathode

Zhang¹,

Ling²

2016

MRS Energy & Sustainability

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Current performance of Mg battery cathode is reviewed. Perspective for research in this fi eld is provided and discussed.Mg battery has recently gathered more and more interest as a high energy density replacement of current Li-ion battery. Signifi cant progress has been made in developing sustainable anode and novel electrolyte. However, the success of Mg battery still high demands the search of cathode material with high energy density, good rate capability, and nice cyclability. This current review focuses on the development of Mg battery cathode in the past 15 years. A detailed review about the performance and limitations of reported cathode material is provided.A perspective for this area is discussed with insights for future research direction. Three important areas that must be explored in this fi eld in near future are suggested: the investigation of high capacity cathode, the study of hybrid ion battery, and deeper understanding about the magnesiation chemistry of the cathode.

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α-MnO2 as a cathode material for rechargeable Mg batteries

Cited by 302 publications

References 18 publications

Electrochemistry of Hollandite α-MnO₂: Li-Ion and Na-Ion Insertion and Li₂O Incorporation

Electrochemistry of Hollandite α-MnO₂: Li-Ion and Na-Ion Insertion and Li₂O Incorporation

Sponge-Like Porous Manganese(II,III) Oxide as a Highly Efficient Cathode Material for Rechargeable Magnesium Ion Batteries

Status and challenge of Mg battery cathode

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α-MnO2 as a cathode material for rechargeable Mg batteries

Cited by 302 publications

References 18 publications

Electrochemistry of Hollandite α-MnO2: Li-Ion and Na-Ion Insertion and Li2O Incorporation

Electrochemistry of Hollandite α-MnO2: Li-Ion and Na-Ion Insertion and Li2O Incorporation

Sponge-Like Porous Manganese(II,III) Oxide as a Highly Efficient Cathode Material for Rechargeable Magnesium Ion Batteries

Status and challenge of Mg battery cathode

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Electrochemistry of Hollandite α-MnO₂: Li-Ion and Na-Ion Insertion and Li₂O Incorporation

Electrochemistry of Hollandite α-MnO₂: Li-Ion and Na-Ion Insertion and Li₂O Incorporation