High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn<sub>2</sub>O<sub>4</sub> Thin Films

Put, Brecht; Vereecken, Philippe M.; Labyedh, Nouha; Sepúlveda, Mauricio; Huyghebaert, Cedric; Radu, Iuliana; Stesmans, André

doi:10.1021/acsami.5b06386

Cited by 62 publications

(81 citation statements)

References 57 publications

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“…On the one hand, novel material chemistries are being investigated, for example, moving from the classical graphite anode to high capacity composites of graphite including silicon, and moving from the original cathode LiCoO 2 to cheaper and safer high‐power cathodes such as spinel LiMn 2 O 4 (LMO), and higher energy compounds such as LiMn 1.5 Ni 0.5 O 4 (LMNO) . On the other hand, the classical lithium ion battery can still be improved to some extent, by nanoscaling the electrodes, moving to complex 3D battery architectures, carbon nanotube or carbon nanosheet based electrodes, and interface engineering …”

Section: Introductionmentioning

confidence: 99%

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO₂ and LiMn₂O₄ Lithium Ion Battery Electrodes

Mattelaer

Vereecken

Dendooven

et al. 2017

Adv Materials Inter

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Interface modification is a heavily investigated method of extending the lifetime of lithium ion batteries. While many studies have explored the effect of interface coating on the lifetime, the rate capability is often overlooked. In this study, the authors investigated the influence of ultrathin (<10 nm) atomic layer deposition (ALD) coatings of amorphous Al2O3 and amorphous TiO2. It is found that, on thin‐film anatase TiO2, the rate capability is unaffected by an amorphous TiO2 coating since it does not pose an additional impedance on the system, while Al2O3 coatings are detrimental for the rate performance due to the 1.5 × 1012 Ω cm resistivity toward lithium ions. A thicker than 2 nm ALD Al2O3 film is found to block lithium transfer completely, resulting in a purely capacitive film. Solvent oxidation is studied on thin‐film LiMn2O4. The authors demonstrate that both coatings can partially solve the solvent decomposition. However, the kinetic bottleneck posed by 1 nm Al2O3 is still greater than the uncoated LiMn2O4, leading to worsened rate capability. ALD TiO2 on the other hand can prevent most of the solvent decomposition, resulting in smoother electrodes. The absence of the decomposition layer and lithium conducting properties of the ALD TiO2 films results in an improved rate capability for the ALD TiO2 coated electrode.

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Section: Introductionmentioning

confidence: 99%

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO₂ and LiMn₂O₄ Lithium Ion Battery Electrodes

Mattelaer

Vereecken

Dendooven

et al. 2017

Adv Materials Inter

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“…LiMn 2 O 4 has a capacity of ≈110 mAh g −1 , while LiCoO 2 and LiFePO 4 have capacities of 140 and 170 mAh g −1 , respectively. [11,12] In order to improve these shortcomings and harness the highrate charge storage in LiMn 2 O 4 , a detailed understanding of the origins of charge storage in nanoscale LiMn 2 O 4 and the factors driving the degradation of LiMn 2 O 4 is needed. [5,7] Recent work has also indicated some reversibility at <3 V in nanoscale LiMn 2 O 4 , which is consistent with our observations below.…”

Section: Introductionmentioning

confidence: 99%

“…[5,7] Recent work has also indicated some reversibility at <3 V in nanoscale LiMn 2 O 4 , which is consistent with our observations below. [11,12] In order to improve these shortcomings and harness the highrate charge storage in LiMn 2 O 4 , a detailed understanding of the origins of charge storage in nanoscale LiMn 2 O 4 and the factors driving the degradation of LiMn 2 O 4 is needed.…”

Section: Introductionmentioning

confidence: 99%

Band Diagram and Rate Analysis of Thin Film Spinel LiMn₂O₄ Formed by Electrochemical Conversion of ALD‐Grown MnO

Young

Schnabel

Holder

et al. 2016

Adv Funct Materials

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Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2 O 4 ) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2 O 4 thin films in electrolytes containing Li + , Na + , K + , and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2 O 4 informed by screened hybrid density functional theory calculations is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2 O 4 . It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2 ) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2 O 4 . Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2 O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. The hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.

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“…In case of LiMn 2 O 4 , two‐step discharge occurs, as indicated by two plateaus appearing at 4.1 V and 3.95 V when cycled against lithiated T‐gCNP. As already reported in literature, in case of LiMn 2 O 4 , the process of lithiation involves the formation of two phases depending on the extent of lithiation . It is possible to discharge LiMn 2 O 4 to a voltage as low as 2.0 V to enable greater extent of Li + ‐ion intercalation.…”

Section: Resultsmentioning

confidence: 83%

Li–Ion‐Conducting Pillar‐Like Graphitic Carbon Nitrides as Novel Anodes for Li–Ion Batteries

2018

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There is still a sustained effort to explore and develop new electrode materials for Li‐ion rechargeable batteries. Presently, materials exploration not only focuses on the enhancement of Li‐ion battery performance, but also targets to make them cheaper and safer. This expectedly will make them market competitive against established battery chemistries. Graphitic carbon nitride (g‐C3N4), which has emerged as an important photon harvesting material, is demonstrated here as a potential efficient and cost effective alternative anode for Li‐ion cells. The g‐C3N4, synthesized here from pyrolysis of thiourea, possesses both graphitic and amorphous phases (T‐gCN). The intercalation of Li+ ions in the densely packed layered structure of T‐gCN (lithiated T‐gCN) results in an ionic conductivity ≈ 10−7 S/cm compared to the non‐lithiated T‐gCN which shows no ionic conductivity. The ionic transport takes place via both the amorphous and graphitic phases in T‐gCN. The T‐gCN when treated with an acidified dichromate solution disintegrates in to filaments, which on prolonged stirring self‐assemble into pillar‐like g‐C3N4 structures (T‐gCNP). The T‐gCNP exhibited higher crystallinity and an even higher ionic conductivity compared to the T‐gCN. The T‐gCN and T‐gCNP deliver modest specific capacities compared to battery grade graphite and other reported carbonaceous/non‐carbonaceous materials in the half‐cell operation. However, when coupled with cathodes such as LiFePO4 and LiMn2O4 in a full Li‐ion cell, the specific capacity obtained in the 1st discharge cycle for both LiFePO4 and LiMn2O4 are very close to their theoretical capacities. The cells display stable cycling and good current rate capability over widely varying current values. This is remarkable in spite of the fact that the samples are not completely crystalline with an average carbon content of approximately 31%. It is envisaged that a continuous network persists for electron transport for their participation in the reversible redox process.

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High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn₂O₄ Thin Films

Cited by 62 publications

References 57 publications

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO₂ and LiMn₂O₄ Lithium Ion Battery Electrodes

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO₂ and LiMn₂O₄ Lithium Ion Battery Electrodes

Band Diagram and Rate Analysis of Thin Film Spinel LiMn₂O₄ Formed by Electrochemical Conversion of ALD‐Grown MnO

Li–Ion‐Conducting Pillar‐Like Graphitic Carbon Nitrides as Novel Anodes for Li–Ion Batteries

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High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn2O4 Thin Films

Cited by 62 publications

References 57 publications

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO2 and LiMn2O4 Lithium Ion Battery Electrodes

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO2 and LiMn2O4 Lithium Ion Battery Electrodes

Band Diagram and Rate Analysis of Thin Film Spinel LiMn2O4 Formed by Electrochemical Conversion of ALD‐Grown MnO

Li–Ion‐Conducting Pillar‐Like Graphitic Carbon Nitrides as Novel Anodes for Li–Ion Batteries

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Product

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High Cycling Stability and Extreme Rate Performance in Nanoscaled LiMn₂O₄ Thin Films

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO₂ and LiMn₂O₄ Lithium Ion Battery Electrodes

The Influence of Ultrathin Amorphous ALD Alumina and Titania on the Rate Capability of Anatase TiO₂ and LiMn₂O₄ Lithium Ion Battery Electrodes

Band Diagram and Rate Analysis of Thin Film Spinel LiMn₂O₄ Formed by Electrochemical Conversion of ALD‐Grown MnO