Sonochemical and soft-chemical intercalation of lithium ions into MnO2 polymorphs

Kumar, V. Ganesh; Gnanaraj, Joe; Salitra, Gregory; Abramov, A. A.; Gedanken, A.; Aurbach, Doron; Soupart, Jean-Bruno; Rousche, J. C.

doi:10.1007/s10008-004-0518-9

Cited by 12 publications

(4 citation statements)

References 24 publications

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“…39 The 1 × 1 tunnels are expected to have limited contribution to the discharge capacity, whereas 2 × 2 tunnels determine the overall discharge capacity in cathodic application of α-MnO 2 nanowires. 40 The bright spots surrounding each tunnel refer to Mn ([MnO 6 ]) atomic columns (yellow dots), whereas the spots in the center of each 2 × 2 tunnel belongs to K ions (pink dots), as confirmed by EDS mapping of K signal in Figure 2i. To the authors' knowledge, this [001] zone axis image is the first atomistic observation of the tunneled structure in α-MnO 2 capturing the position of tunnel stabilizers.…”

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confidence: 78%

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Asynchronous Crystal Cell Expansion during Lithiation of K⁺-Stabilized α-MnO₂

et al. 2015

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α-MnO2 is a promising material for Li-ion batteries and has unique tunneled structure that facilitates the diffusion of Li(+). The overall electrochemical performance of α-MnO2 is determined by the tunneled structure stability during its interaction with Li(+), the mechanism of which is, however, poorly understood. In this paper, a novel tetragonal-orthorhombic-tetragonal symmetric transition during lithiation of K(+)-stabilized α-MnO2 is observed using in situ transmission electron microscopy. Atomic resolution imaging indicated that 1 × 1 and 2 × 2 tunnels exist along c ([001]) direction of the nanowire. The morphology of a partially lithiated nanowire observed in the ⟨100⟩ projection is largely dependent on crystallographic orientation ([100] or [010]), indicating the existence of asynchronous expansion of α-MnO2's tetragonal unit cell along a and b lattice directions, which results in a tetragonal-orthorhombic-tetragonal (TOT) symmetric transition upon lithiation. Such a TOT transition is confirmed by diffraction analysis and Mn valence quantification. Density functional theory (DFT) confirms that Wyckoff 8h sites inside 2 × 2 tunnels are the preferred sites for Li(+) occupancy. The sequential Li(+) filling at 8h sites leads to asynchronous expansion and symmetry degradation of the host lattice as well as tunnel instability upon lithiation. These findings provide fundamental understanding for appearance of stepwise potential variation during the discharge of Li/α-MnO2 batteries as well as the origin for low practical capacity and fast capacity fading of α-MnO2 as an intercalated electrode.

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confidence: 78%

“…This definition is based on the number of [MnO 6 ] octahedra in each side . The 1 × 1 tunnels are expected to have limited contribution to the discharge capacity, whereas 2 × 2 tunnels determine the overall discharge capacity in cathodic application of α-MnO 2 nanowires …”

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confidence: 99%

Asynchronous Crystal Cell Expansion during Lithiation of K⁺-Stabilized α-MnO₂

et al. 2015

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“…Also, LiMn 2 O 4 was synthesized by sonochemical and chemical intercalation of Li ion into different polymorphs of MnO 2 , proving that the nature of MnO 2 affects the degree of lithiation and purity of the spinel LiMn 2 O 4 . [ 79 ] Likewise, low‐temperature lithium intercalation and postheat treatment made it possible to reduce nickel/lithium site exchange in Nickel‐rich lithium transition metal oxides in comparison to the traditional solid‐state synthesis method. [ 80 ] In doing so, the ability of small alkali ions to be mobile in these structures at low temperature via chemical intercalation is being exploited to avoid high‐temperature sintering and maintain low‐entropy structures and small particle sizes.…”

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confidence: 99%

A Review of Chemically Induced Intercalation and Deintercalation in Battery Materials

Odetallah

Kuß

2023

Energy Tech

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Intercalation is the fundamental process underlying lithium‐ion batteries and related technologies. While intercalation is electrochemically induced in batteries, it can also be performed with chemical redox agents. In principle, the two processes are equivalent, although there can be differences, such as rate control, side reactions, and charge transfer mechanisms. Chemically induced intercalation can be used where electrochemical methods are impractical or impossible and continues to inspire innovative applications. This chemistry is important in synthesis and pretreatment of intercalation materials, with novel impactful applications emerging that range from lithium recycling to intercalation material‐based redox flow batteries. This review summarizes the use of chemical intercalation and serves as a resource for selecting and optimizing methods specific to material and application. Covering the whole life cycle of intercalation materials: development, synthesis, use, and finally recycling, it can be expected that these reactions will continue to have great impact on the path toward efficient and cheap energy storage.

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“…This morphology is typical of tunnel-containing manganese oxides such as hollandites (''a-MnO 2 ''), which have tetragonal (or distorted tetragonal) symmetry with c/a # 4, in agreement with the observed morphology. 33,34 These crystals are a minority phase and were not investigated further.…”

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confidence: 99%

Structural and electrochemical properties of new nanospherical manganese oxides for lithium batteries

et al. 2005

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The products of decomposition of manganese carbonate with and without doping by copper or cobalt, at temperatures ,500 uC in air were studied. Doped systems with 20 atom% Cu or Co give new nanometric manganese oxides agglomerated in submicronic spheres at 370 uC. Transmission electron microscopy (TEM) shows that these X-ray amorphous compounds are nanocrystalline with grain size in the 10 nm range and a spinel substructure. The electrochemical behaviour of these materials in lithium cells was studied. Whereas non-doped manganese oxide exhibits poor intercalation capabilities, the freshly co-precipitated Cu or Co doped materials can be cycled successfully around 3 V vs. Li/Li + . Step-potential electrochemical spectroscopy shows that the initial discharge gives rise to a two-phase transition and is followed by stable, reversible, singlephase cycling. Best results are obtained on a cobalt-doped manganese oxide (Co : Mn 5 1 : 5), which can sustain more than 100 charge-discharge cycles with a 175 mA h g 21 capacity in the 1.8-4.2 V range. XAS spectra were measured on pristine and electrochemically discharged materials, showing that (1) in the cobalt-doped material, cobalt is divalent and manganese is the only redox-active species, (2) the variations in local structure around Mn on discharge are much smaller than in long-range ordered compounds such as Li-Mn-O spinels.

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Sonochemical and soft-chemical intercalation of lithium ions into MnO2 polymorphs

Cited by 12 publications

References 24 publications

Asynchronous Crystal Cell Expansion during Lithiation of K⁺-Stabilized α-MnO₂

Asynchronous Crystal Cell Expansion during Lithiation of K⁺-Stabilized α-MnO₂

A Review of Chemically Induced Intercalation and Deintercalation in Battery Materials

Structural and electrochemical properties of new nanospherical manganese oxides for lithium batteries

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Sonochemical and soft-chemical intercalation of lithium ions into MnO2 polymorphs

Cited by 12 publications

References 24 publications

Asynchronous Crystal Cell Expansion during Lithiation of K+-Stabilized α-MnO2

Asynchronous Crystal Cell Expansion during Lithiation of K+-Stabilized α-MnO2

A Review of Chemically Induced Intercalation and Deintercalation in Battery Materials

Structural and electrochemical properties of new nanospherical manganese oxides for lithium batteries

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Product

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Asynchronous Crystal Cell Expansion during Lithiation of K⁺-Stabilized α-MnO₂

Asynchronous Crystal Cell Expansion during Lithiation of K⁺-Stabilized α-MnO₂