Lithium Aluminum Manganese Oxide Having Spinel-Framework Structure for Long-Life Lithium-Ion Batteries

Ariyoshi, Kingo; Iwata, Eiichi; Kuniyoshi, Minoru; Wakabayashi, Hiromichi; Ohzuku, Tsutomu

doi:10.1149/1.2360019

Cited by 63 publications

(66 citation statements)

References 29 publications

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“…In order to improve the performance of such batteries, the cubic phase is stabilized by substitution of Mn with other elements. 1,22 The effects of such substitution on the lattice stability are usually examined by XRD and/or DSC measurements. However, the fact that + SR is able to provide information on the appearance of the short-range cooperative JT distortion, the only technique to our knowledge that is able to do so, suggests that substitution effects in LMO should be reexamined by combining + SR and electrochemical analyses.…”

Section: Discussionmentioning

confidence: 99%

Microscopic magnetic and structural nature of spinelLi[LixMn2−x]O4

et al. 2007

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The magnetic nature of the spinel antiferromagnet Li͓Li x Mn 2−x ͔O 4 with x = 0 -0.15 has been studied with muon-spin rotation and relaxation ͑ + SR͒ spectroscopy. Both weak-transverse-field and zero-field + SR measurements indicate that the whole sample enters into a static disordered magnetic phase below T N for all the samples measured; T N = 61 K for LiMn 2 O 4 , but 27-23 K for the x = 0.05-0.15 samples. It was also clarified that both the field distribution width and the field fluctuation rate show a clear change at the Jahn-Teller ͑JT͒ transition temperature ͑T JT = 280 K͒ for LiMn 2 O 4 , and a short-range cooperative JT distortion appears below 280 K even for Li͓Li 0.15 Mn 1.85 ͔O 4 .

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Section: Discussionmentioning

confidence: 99%

Microscopic magnetic and structural nature of spinelLi[LixMn2−x]O4

et al. 2007

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“…[1][2][3][4] It combines the highest intrinsic rate capability of the well-known intercalation cathodes with high safety, low toxicity, and low cost, making it attractive for high-power applications, such as hybrid electric vehicles. [5][6][7][8][9][10][11] However, the drawback of this electrode is its slow dissolution in the electrolyte present in the lithium-ion battery. To mitigate such dissolution, recent interest has focused on highly lithium-rich compositions in the region of Li 1. [11,12] Consequently, high rate capability becomes even more important to ensure high utilization of the reduced theoretical capacity.…”

mentioning

confidence: 99%

“…[5][6][7][8][9][10][11] However, the drawback of this electrode is its slow dissolution in the electrolyte present in the lithium-ion battery. To mitigate such dissolution, recent interest has focused on highly lithium-rich compositions in the region of Li 1. [11,12] Consequently, high rate capability becomes even more important to ensure high utilization of the reduced theoretical capacity. Here we describe the synthesis of an ordered mesoporous Li 1.12 Mn 1.88 O 4 spinel and show that it combines higher rate capability than the corresponding bulk material (50 % higher specific capacity at a rate of 30C, 3000 mA g À1 ) at ambient temperature with good stability at elevated temperatures, despite a high surface area of 90 m 2 g À1 and without the need for deliberate coating or doping with foreign ions.…”

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confidence: 99%

Synthesis of Ordered Mesoporous Li–Mn–O Spinel as a Positive Electrode for Rechargeable Lithium Batteries

et al. 2008

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LiMn 2 O 4 spinel is one of the most important intercalation electrodes for rechargeable lithium batteries at the present time. [1][2][3][4] It combines the highest intrinsic rate capability of the well-known intercalation cathodes with high safety, low toxicity, and low cost, making it attractive for high-power applications, such as hybrid electric vehicles. [5][6][7][8][9][10][11] However, the drawback of this electrode is its slow dissolution in the electrolyte present in the lithium-ion battery. To mitigate such dissolution, recent interest has focused on highly lithium-rich compositions in the region of Li 1. [11,12] Consequently, high rate capability becomes even more important to ensure high utilization of the reduced theoretical capacity. Here we describe the synthesis of an ordered mesoporous Li 1.12 Mn 1.88 O 4 spinel and show that it combines higher rate capability than the corresponding bulk material (50 % higher specific capacity at a rate of 30C, 3000 mA g À1 ) at ambient temperature with good stability at elevated temperatures, despite a high surface area of 90 m 2 g À1 and without the need for deliberate coating or doping with foreign ions. [13,14] Furthermore, when cycled over a wide voltage range (including the 3 V and 4 V plateaus) the mesoporous material exhibits improved capacity retention compared to the bulk spinel. This capacity retention is because of the nanometer thin walls between the pores that render the cubic/tetragonal phase transformation more facile in the mesoporous spinel than in the bulk phase. The potential advantages of using nanostuctured electrode materials, in this case mesoporous solids, over nanoparticles are discussed.Ordered mesoporous Li 1+x Mn 2Àx O 4 spinel is synthesized for the first time, as described in detail in the Experimental Section, by a hard templating route with post-template treatment .[ [15][16][17][18][19] Briefly, an aqueous solution of Mn(NO 3 ) 2 was infiltrated into the ordered 3D pore structure of the mesoporous silica, KIT-6. Heating in air converted the precursor into Mn 2 O 3 . Following the removal of the SiO 2 template, the replica 3D mesoporous Mn 2 O 3 was transformed to Mn 3 O 4 spinel by heating in a reducing atmosphere, which then reacted with LiOH to form mesoporous LiMn 2 O 4 spinel (Figure 1). It is remarkably that throughout the solid-state transformations Mn 2 O 3 !Mn 3 O 4 !LiMn 2 O 4 , the ordered 3D mesoporous structure was preserved (Figure 1), demonstrating that the thin walls of the mesopore (7 nm thick) can accommodate the strain of multiple solid-solid phase transformations. The mesoporous structure exists throughout the material, as demonstrated by examining many particles using

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“…In all cases, they are higher than those determined for LiMn 2 O 4 (Fig. 6a, Table 2), and they are among the best values reported in the literature for LiMn 2 O 4 -based cathodes [10,13,15,[38][39][40]. It is worth to mention that at 55 • C the y = 0.06 spinels also show good capacity retention (Fig.…”

Section: Electrochemical Propertiesmentioning

confidence: 47%

“…So, in our opinion, the LiMn 1.93 Li 0.06 Ni 0.01 O 4 and LiMn 1.93 Li 0.06 Al 0.01 O 4 , that have capacities of ≈105 mAh g −1 and ciclabilities of ≈99.9% by cycle, are the two spinels that better fulfil both capacity and cycling performance requirements at high temperature. It is worth to mention that the Q d and cc values shown by these samples are among the best reported for LiMn 2 O 4 -based spinels [10,13,15,[38][39][40], indicating that they are very well suited materials for application as cathode in Liion batteries working even at high temperature. Furthermore, the remarkable rate capability exhibited by the LiMn 1.99−y Li y M 0.01 O 4 spinels, coupled with the low cost and low toxicity of these compounds, makes them very attractive for hybrid and electric vehicles.…”

Section: Electrochemical Propertiesmentioning

confidence: 77%