Manganese Vanadates and Molybdates as Anode Materials for Lithium-Ion Batteries

Wakihara, Masataka; Ikuta, Hiromasa; Uchimoto, Yoshiharu

doi:10.1007/0-306-47508-1_4

Cited by 48 publications

(64 citation statements)

References 32 publications

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“…The reported two distinguishable lattice parameters in the region of 0.5 Ͼ x Ͼ 0.1 are related to the Li-rich ͑L 0.5 Mn 2 O 4 ͒ and Li-poor ͑MnO 2 ͒ characteristics. 1 The Mn 4+ -aggregated domain corresponds to MnO 2 in XRD analysis. If the Mn 4+ domain grows gradually from the center, Li ions must be deintercalated from the growing point of the domain, which means that there is no selectivity of the deintercalated site.…”

Section: A17mentioning

confidence: 99%

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Configurational Entropy of Lithium Manganese Oxide and Related Materials, LiCr[sub y]Mn[sub 2−y]O[sub 4] (y=0, 0.3)

Kobayashi¹,

Mita²,

Seki³

et al. 2008

J. Electrochem. Soc.

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The change in entropy of Li x Cr y Mn 2−y O 4 ͑y = 0, 0.3͒, ⌬S, was determined by potentiometric and calorimetric approaches. The ⌬S obtained by the two different methods showed similar trends. The peak in ⌬S was explained by the partial Li-ion ordering of the Li͑1͒͑0, 0, 0͒ and Li͑2͒͑0.25, 0.25, 0.25͒ sites in the sublattice of the 8a site at x = 0.6. The following complete ordering at x = 0.5 was accompanied with the rearrangement of the partial ordering between Li͑1͒ and Li͑2͒. Although the ⌬S peak was diminished by partial Cr-ion substitution because of the incomplete ordering due to the random dispersion of Cr ions, the peak position ͑x͒ of ⌬S remained unchanged. This suggested that the voltage step between 0.6 Ͼ x Ͼ 0.5 in Li x Cr y Mn 2−y O 4 was not due to the structural change in the host spinel structure but mainly caused by the Li-ion partial ordering at x = 0.6, the rearrangement of the two domains ͑0.6 Ͼ x Ͼ 0.5͒, and the following perfect ordering ͑x = 0.5͒. 3 The derivative of OCP with respect to temperature, dE/dT, is proportional to ⌬S. They obtained ⌬S at each state of charge ͑SOC͒ and found a marked change from positive to negative values at approximately x = 0.5 for Li x Mn 2 O 4 . However, the actual positive peak of dE/dT was observed before x = 0.5 during charging. Another approach to determining ⌬S is the calorimetric method.4 Kim et al. reported the heat flow of the ͓Li͉Li x Mn 2 O 4 ͔ coin-type cell by calorimetry with a sufficient signal level.5 They also found a marked peak in heat flow at approximately x = 0.45 and 0.55. In addition, they proposed a correlation between the phase diagrams of the host Li x Mn 2 O 4 structure. They used phase diagrams obtained by in situ synchrotron X-ray diffraction ͑XRD͒ analysis 6 and noted that it changes from endothermic to exothermic in the two-phase region ͑0.9 Ͼ x Ͼ 0.55, 0.45 Ͼ x Ͼ 0.15͒ while heat flow changes from exothermic to endothermic in the single-phase region ͑0.55 Ͼ x Ͼ 0.45͒. They explained that heat generation occurs as a result the phasetransformation process, which produces a disordered two-phase region. However, thermal profiles, such as those of endothermic to exothermic changes, were generally explained in terms of the singlephase region using a configurational entropy change.7 Furthermore, similar thermal profiles were reported by Bang et al. in Alsubstituted LiAl 0.17 Mn 1.83 O 3.97 S 0.03 . 8 In general, substituting Mn with a metal suppresses the phase change. If the heat flow has a strong correlation to the host structure, the specific thermal character should be further suppressed. Partially Cr-substituted LiCr 0.3 Mn 1.7 O 4 is known to be a material that remains the single phase during Li intercalation/deintercalation of the host structure.9 It is meaningful to compare the entropy change between multiphase coexisting LiMn 2 O 4 and single-phase LiCr 0.3 Mn 1.7 O 4 . In particular, it is important to clarify which is the dominant factor for the change voltage, the host structure or the configurational entropy. In this st...

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Section: A17mentioning

confidence: 99%

“…1 LiMn 2 O 4 has a two-plateau voltage profile in the 4.0 and 4.1 V regions. Gao et al predicted the two-plateau profile to be an order-disorder phase transition of Li ions using a simple lattice gas model.…”

mentioning

confidence: 99%

Configurational Entropy of Lithium Manganese Oxide and Related Materials, LiCr[sub y]Mn[sub 2−y]O[sub 4] (y=0, 0.3)

Kobayashi¹,

Mita²,

Seki³

et al. 2008

J. Electrochem. Soc.

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“…Introduced in 1983 by J. B. Goodenough [6], Li x Mn 2 O 4 serves as an attractive alternative to Li x CoO 2 in terms of environmental friendliness, cost effectiveness, safety [7], as well as with its virtue to enable the variation of the lithium stoichiometry x over the entire range from 0 to 1. When x = 0, the battery is said to be in a completely charged state, while x = 1 implies the battery is totally discharged.…”

Section: Introductionmentioning

confidence: 99%

Correlation between battery material performance and cooperative electron-phonon interaction in LiCoyMn2-yO4

Ragavendran

Mandal

Yarlagadda

2017

Applied Physics Letters

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Understanding the basic physics related to archetypal lithium battery material (such as LiCoyMn2−yO4) is of considerable interest and is expected to aid designing of cathodes of high capacity. The relation between electrochemical performance, activated-transport parameters, thermal expansion, and cooperativity of electron-phonon-interaction distortions in LiCoyMn2−yO4 is investigated. The first order cooperative-normal-mode transition, detected through coefficient of thermal expansion, is found to disappear at a critical doping (y ∼ 0.16); interestingly, for y > ∼ 0.16 the resistivity does not change much with doping and the electrochemical capacity becomes constant over repeated cycling. The critical doping y ∼ 0.16 results in breakdown of the network of cooperative/coherent normal-mode distortions; this leads to vanishing of the first-order transition, establishment of hopping channels with lower resistance, and enhancing lithiation and delithiation of the battery, thereby minimizing electrochemical capacity fading.

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“…1,2 For practical applications, particularly in electric vehicles, a higher rate capability, in addition to a higher energy density, is one of the most important characteristics, and it mainly depends on the electrode materials. [3][4][5] However, lithium-ion cells cycled at a relatively high current density exhibit a significant power loss, which is primarily associated with a rise in the positive electrode impedance; some active particles became electrically disconnected with the remaining part of the positive electrode.…”

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confidence: 99%

“…The temperature was then maintained for 5 min, the current was switched off, the pressure was released, and the sample was cooled to room temperature. The resulting products were crushed and ground with a mortar for more than 15 min and then used for characterization ͑Li 1 The phase purity of the samples was checked by X-ray diffractometry ͑XRD; Rigaku Rotaflex RU-200B/RINT using monochromatic Cu K␣ radiation͒. The particle size was checked by fieldemission scanning electron microscopy ͑FE-SEM; Hitachi S-5000͒, and the size distribution was measured by a laser diffraction and scattering method ͑Shimadzu SALD-2000͒.…”

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confidence: 99%

Preparation of Dense Li[sub 1.05]Mn[sub 1.95]O[sub 4]∕C Composite Positive Electrodes Using Spark-Plasma-Sintering-Process

Takeuchi

Tabuchi

Nakashima

et al. 2005

Electrochem. Solid-State Lett.

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Composite electrodes ͑positive electrode active materials/carbon͒, applicable for rechargeable lithium-ion batteries cycled at a high current density, were prepared using the spark-plasma-sintering ͑SPS͒ technique. Li 1.05 Mn 1.95 O 4 /C composite electrodes with a carbon content of 10 wt % were synthesized at 300°C using SPS, and it was found that Li 1.05 Mn 1.95 O 4 particles were covered with fine carbon particles and formed agglomerates with the size of ϳ10 m. This resulted in a higher electrode density. Charge/ discharge tests of cells using the Li 1.05 Mn 1.95 O 4 /C composite cathodes showed superior cycle performances at the rates of 30 -148 mA g −1 ͑0.2-1 C͒ compared with the cell using the conventionally prepared Li 1.05 Mn 1.95 O 4 + C cathode. The improvement in the cell performance was attributed to the strong binding between the Li 1.05 Mn 1.95 O 4 and carbon powders. Consequently, the electrical network remained almost unchanged during the electrochemical redox cycling even at a high current rate.Lithium-ion batteries have been extensively studied for use in portable electronics and electric vehicles due to their relatively high specific energy and power. 1,2 For practical applications, particularly in electric vehicles, a higher rate capability, in addition to a higher energy density, is one of the most important characteristics, and it mainly depends on the electrode materials. 3-5 However, lithium-ion cells cycled at a relatively high current density exhibit a significant power loss, which is primarily associated with a rise in the positive electrode impedance; some active particles became electrically disconnected with the remaining part of the positive electrode. 3,4 This could be attributed partly to mechanical stress caused by their volumetric changes during insertion/extraction of the lithium ions, and/or partly to the detachment of the conductive additives from the active materials. Such detachment of the conductive additives is a serious problem even for relatively high-conductive positive electrodes such as LiNi 0.8 Co 0.2 O 2 , 3,4 and a method to overcome this problem is required irrespective of the active materials.Recently, the introduction of conductive additives, such as a carbon coating on the surface of the olivine compound, LiFePO 4 , and spinel compound, LiMn 2 O 4 , has been reported to be effective for successfully improving the cell specific capacity even at a high current density. 6-10 Although the carbon coating was effective for improving the cell specific capacities, it usually decreased the cathode density due to their bulky volume, which could lower the cell volumetric energy. For practical applications, improvement of both the specific capacity and electrode density is required, but there have been few reports on the simultaneous improvement of these two factors.Spark-plasma-sintering ͑SPS͒, also called pulse electric current sintering, is a process that makes use of a microscopic electrical discharge between particles. 11 In this process, the powders loaded in the gr...

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Manganese Vanadates and Molybdates as Anode Materials for Lithium-Ion Batteries

Cited by 48 publications

References 32 publications

Configurational Entropy of Lithium Manganese Oxide and Related Materials, LiCr[sub y]Mn[sub 2−y]O[sub 4] (y=0, 0.3)

Configurational Entropy of Lithium Manganese Oxide and Related Materials, LiCr[sub y]Mn[sub 2−y]O[sub 4] (y=0, 0.3)

Correlation between battery material performance and cooperative electron-phonon interaction in LiCoyMn2-yO4

Preparation of Dense Li[sub 1.05]Mn[sub 1.95]O[sub 4]∕C Composite Positive Electrodes Using Spark-Plasma-Sintering-Process

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