Effects of Partial Acid Delithiation on the Electrochemical Lithium Insertion Properties of Nickel-Stabilized LiMn2O4 Spinel Oxides

Lavela, Pedro; Sánchez, L.; Tirado, J.L.; Bach, S.; Pereira-Ramos, J.P.

doi:10.1006/jssc.1999.8583

Cited by 10 publications

(5 citation statements)

References 25 publications

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“…21 In this case, the insertion of protons results in a vibration at 938 cm -1 , due to a lattice coupling of the H + -form spinel. 21,33,34 In the case of H + insertion in the perovskite structure, this lattice coupling mode of the proton could explain the vibration at 922 cm -1 , observed in AGED LLTO and samples exchanged in water (Li 0.30-y H y ) La 0.57 TiO 3 .…”

Section: Resultsmentioning

confidence: 95%

Reaction mechanisms of Li0.30La0.57TiO3 powder with ambient air: H+/Li+ exchange with water and Li2CO3 formation

et al. 2010

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The proton/lithium exchange property of the lithium lanthanum titanate Li(0.30)La(0.57)TiO(3) (named LLTO) is shown to occur at room temperature under ambient air. The (1)H and (7)Li MAS NMR, TGA analysis and IR spectroscopy techniques are used to probe reaction mechanisms. XRPD analysis gives evidence of the topotactic character of this exchange reaction. As for exchange in aqueous solution, it is shown that Li(0.30)La(0.57)TiO(3) is able to dissociate water on the grain surface and then to exchange H(+) for Li(+) into the perovskite structure. Lithium hydroxide is then formed on the grain surface and afterwards reacts with CO(2) contained in air to form Li(2)CO(3). It is shown that this mechanism is reversible. When the aged sample (aging in air for 5 months at room temperature) is annealed at 400 degrees C for two hours, the initial LLTO sample is totally recovered, a mass loss is observed and the carbonate signal in IR spectra disappears, demonstrating the reversibility of the carbonation reaction process.

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Section: Resultsmentioning

confidence: 95%

Reaction mechanisms of Li0.30La0.57TiO3 powder with ambient air: H+/Li+ exchange with water and Li2CO3 formation

et al. 2010

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“…Also, the chemical delithiation from the spinel may induce small amounts of Mn 2+ dissolution via a disproportionation of Mn 3+ . [54][55][56] This would also raise the average oxidation state, increase the OCV, and shrink the unit cell by the formation of Mn 4+ . As discussed above, an exchange during acid exposure results in the formation of adsorbed water and hydroxyl groups in the spinel structure.…”

Section: ͓1͔mentioning

confidence: 99%

Electrochemical Performance of Acid-Treated Nanostructured LiMn[sub 1.5]Ni[sub 0.5]O[sub 4−δ] Spinel at Elevated Temperature

Hagh¹,

Cosandey²,

Rangan³

et al. 2010

J. Electrochem. Soc.

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A surface treatment process based on a mild acidic solution was utilized to stabilize the surface of the LiMn1.5Ni0.5normalO4−δ (LMNO) spinel cathode material and to improve its elevated temperature performance. To characterize the failure mechanism of the LMNO spinel at an elevated temperature (60°C) , the effect of the Mn3+ content and the charge/discharge state storage conditions were studied. It was shown that the existence of Mn3+ is necessary for an improved elevated temperature performance. It was also identified that one of the main degradation mechanisms at an elevated temperature was the systematic impedance rise rather than the intrinsic capacity loss. The results of the charged state storage at 60°C demonstrated the worst condition for the spinel materials; however, the surface-treated materials presented an improved elevated temperature cycling and a much less impedance increase than the untreated spinel after 4 weeks of storage at 60°C . X-ray diffraction, X-ray photoelectron spectroscopy, high resolution transmission electron microscopy, and electron energy loss spectroscopy were utilized to characterize the effect of surface treatment on the crystal structure and morphology of the acid-treated material.

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“…3 In order to overcome this drawback several solutions have been proposed in the literature, such as new preparative routes 4,5 and the use of dopant elements. 6,7 On the other hand, the use of anodic materials as alternatives to graphite, such as tin and/or antimony compounds 8 or transition metal oxides, 9,10 has revealed interesting possibilities for achieving large capacity values for an elevated number of cycles. Many of the new electroactive materials possess significantly higher working potentials than graphite.…”

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confidence: 99%

New LiNi[sub y]Co[sub 1−2y]Mn[sub 1+y]O[sub 4] Spinel Oxide Solid Solutions as 5 V Electrode Material for Li-Ion Batteries

Alcántara

Jaraba²,

Lavela³

et al. 2004

J. Electrochem. Soc.

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New mixed spinel oxides with LiNiyCo1−2yMn1+yO4 false(y=0.2, 0.3, and 0.4) stoichiometries have been synthesized under different annealing temperatures and tested as cathode materials in lithium batteries. High-purity cubic spinel-phase products were obtained between 700 and 950°C, in which the lattice parameter increases with nickel content. The structural and textural properties of the powder samples were studied by X-ray diffraction (XRD) and scanning electron microscopy and correlated with the electrochemical behavior. From these experiments, the best performance was obtained for LiNi0.4Co0.2Mn1.4O4 cathodes with 1-5 μm regular octahedral particles, which developed capacity values close to 120 mAh/g with a good capacity retention. The ex situ XRD patterns of the partially charged electrodes were characteristic of a single cubic phase in which lattice parameter decrease with lithium extraction for all compositions. © 2003 The Electrochemical Society. All rights reserved.

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Effects of Partial Acid Delithiation on the Electrochemical Lithium Insertion Properties of Nickel-Stabilized LiMn2O4 Spinel Oxides

Cited by 10 publications

References 25 publications

Reaction mechanisms of Li0.30La0.57TiO3 powder with ambient air: H+/Li+ exchange with water and Li2CO3 formation

Reaction mechanisms of Li0.30La0.57TiO3 powder with ambient air: H+/Li+ exchange with water and Li2CO3 formation

Electrochemical Performance of Acid-Treated Nanostructured LiMn[sub 1.5]Ni[sub 0.5]O[sub 4−δ] Spinel at Elevated Temperature

New LiNi[sub y]Co[sub 1−2y]Mn[sub 1+y]O[sub 4] Spinel Oxide Solid Solutions as 5 V Electrode Material for Li-Ion Batteries

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