A High-Rate Manganese Oxide for Rechargeable Lithium Battery Applications

Doeff, Marca M.; Anapolsky, Abraham; Edman, Ludvig; Richardson, Thomas J.; Jonghe, Lutgard C. De

doi:10.1149/1.1349883

Cited by 72 publications

(66 citation statements)

References 18 publications

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“…After reaction for 30 min, the peaks at 600 nm and 545 nm were attenuated to 42% and 27% of their original levels, respectively. By contrast, Na 0.44 MnO 2 powder obtained from a solid state reaction [4] showed much poorer reactivity (dashed line). In a control experiment, when no nanowire catalyst was added, the spectrum stayed unchanged after the same reaction period.…”

Section: Nano Researchmentioning

confidence: 98%

Formation of Na0.44MnO2 nanowires via stress-induced splitting of birnessite nanosheets

2009

Nano Res.

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High aspect ratio Na 0.44 MnO 2 nanowires with a complex one-dimensional (1 D) tunnel structure have been synthesized. We found that the reaction went through layered birnessite nanosheet intermediates, and that their conversion to the fi nal product involved splitting of the nanosheets into nanowires. Based on our observations, a stress-induced splitting mechanism for conversion of birnessite nanosheets to Na 0.44 MnO 2 nanowires is proposed. The fi nal and intermediate phases show topotaxy with 001 f // 020 b or 110 b where f represents the fi nal Na 0.44 MnO 2 phase and b the intermediate birnessite phase. As a result of their high surface areas, the nanowires are effi cient catalysts for the oxidation of pinacyanol chloride dye. KEYWORDSBirnessite, manganese oxide, nanowire, nanosheet, stress, conversion Manganese oxide nanowires with layered or tunnel structures are attractive for applications in batteries, separation and catalysis due to their open-framework structures and interesting redox properties [1 9]. There have been several studies of their synthesis in the literature: for example, MnO 2 nanorods were synthesized through a carefully controlled hydrothermal reaction by oxidizing MnSO 4 with (NH 4 ) 2 S 2 O 8 or KMnO 4 [10,11]. Nanowires with cryptomelane [12], romanechite [6,13], and RUB 7 [13 15] structures have also been produced in aqueous solution. Most of these approaches involved a birnessite phase observed as an intermediate [11] or used as precursor [6, 13 15]. Birnessite possesses a layered structure formed of edge-sharing MnO 6 octahedra with Na + cations and H 2 O molecules filling the interlayer space ( Fig. 1 (a)). Conversion of birnessite has been used as a general strategy to obtain a variety of tunnel structures [1]. However, the underlying mechanism remains unclear. Recently, the curling or rolling up of birnessite layers as a result of weakened interlayer interactions during hydrothermal treatment was proposed [11]. While this mechanism can explain tube formation from exfoliated molecular sheets, it cannot rationalize the formation of non-hollow manganese oxide nanowires.Herein we report a stress-induced splitting mechanism that transforms birnessite nanosheets into Na 0.44 MnO 2 nanowires. Na 0.44 MnO 2 has a complex tunnel structure. It consists of columns of edge-sharing MnO 5 square pyramids and sheets of edge-sharing MnO 6 octahedra extending parallel to the c-axis (Fig. 1 (b)). They are connected by cornerNano Res (2009) sharing to form two types of tunnels: large S-shaped, and six-sided tunnels, both occupied by Na + cations.In our study, Na 0.44 MnO 2 nanowires were synthesized by a hydrothermal method. Their X-ray diffraction (XRD) pattern shows diffraction peaks in good agreement with the standard pattern (PDF No. 27 0750), except for some variation in peak intensities due to nanowire orientation ( Fig. 2(a)). An scanning electron microscopy (SEM) image reveals that they are pure nanowires with average length over 10 μm and diameter smaller than 100 nm (Fig. 2(b)...

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Section: Nano Researchmentioning

confidence: 98%

Formation of Na0.44MnO2 nanowires via stress-induced splitting of birnessite nanosheets

2009

Nano Res.

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“…Manganese oxides are potential candidates, but the most common variant based on a spinel structure suffers from a rapid capacity fade at elevated temperatures due to manganese dissolution [1]. Others phases of manganese oxides have also been considered, such as those with tunnel [2] or layered structures [3], [4]. For applications requiring high energy density, layered compounds are the most promising because of the potential for high capacity.…”

Section: Introductionmentioning

confidence: 99%

Investigation of layered intergrowth LixMyMn1?yO2+z (M=Ni, Co, Al) compounds as positive electrodes for Li-ion batteries

et al. 2004

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TitleInvestigation of layered intergrowth LixMyMn1-yO2+z (M=Ni,Co,Al) compounds as positive electrodes for Li-ion batteries electrodes may be prepared from the corresponding sodium manganese metal oxide compounds by ion-exchange. Stacking arrangements (O2, O3, or O2/O3 intergrowths) in the lithiated materials are dependent upon the Na/transition metal ratio in the sodium-containing precursors, the degree of substitution, and the identity of the substituting metal. O3 layered materials deliver up to 200 mAh/g at moderate current densities in lithium cell configurations, but convert rapidly to spinels upon cell cycling, while O2 compounds are more stable but deliver less capacity.Intergrowths show intermediate behavior, with higher capacities than pure O2 materials and better phase stability than O3 compounds. Some intergrowth structures do not appear to convert to spinel during normal cycling, suggesting it may be possible to tailor high energy density, phase stable layered manganese oxide electrodes for lithium batteries.

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“…The excellent cycling stability of tunnel compounds with the Na 0.44 MnO 2 structure using liquid electrolytes at room temperature, or polymer electrolytes at elevated temperatures has been previously noted [25]. Dissolution at elevated temperature in liquid electrolytes is, however, so significant (~5-20 ppm Mn 2+ after two weeks) for unsubstituted Li 0.36 MnO 2 that the storage test was terminated early.…”

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confidence: 75%

Effect of structure on the storage characteristics of manganese oxide electrode materials

Park

Doeff

2007

Journal of Power Sources

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Eleven types of manganese-containing electrode materials were subjected to longterm storage at 55°C in 1M LiPF 6 ethylene carbonate/dimethyl carbonate (EC/DMC) solutions. The amount of manganese dissolution observed depended upon the sample surface area, the average Mn oxidation state, the structure, and substitution levels of the manganese oxide. In some cases, structural changes such as solvate formation were exacerbated by the high temperature storage, and contributed to capacity fading upon cycling even in the absence of significant Mn dissolution. The most stable materials appear to be Ti-substituted tunnel structures and mixed metal layered oxides with Mn in the +4 oxidation state.

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A High-Rate Manganese Oxide for Rechargeable Lithium Battery Applications

Cited by 72 publications

References 18 publications

Formation of Na0.44MnO2 nanowires via stress-induced splitting of birnessite nanosheets

Formation of Na0.44MnO2 nanowires via stress-induced splitting of birnessite nanosheets

Investigation of layered intergrowth LixMyMn1?yO2+z (M=Ni, Co, Al) compounds as positive electrodes for Li-ion batteries

Effect of structure on the storage characteristics of manganese oxide electrode materials

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