The elevated temperature performance of the LiMn2O4/C system: failure and solutions

Amatucci, Glenn G.; Pasquier, Aurelien Du; Blyr, A.; Zheng, Tao; Tarascon, Jean‐Marie

doi:10.1016/s0013-4686(99)00209-1

Cited by 287 publications

(213 citation statements)

References 37 publications

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“…[1][2][3][4][5][6] To improve its cycling performance, especially at elevated temperature (¢50 uC), several approaches such as doping at the Mn site, surface modification, and various preparatory conditions have been shown to be successful. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] The partial substitution of Mn as Li(M,Mn) 2 O 4 , (M~Li, Co, Cr, Al, (Co,Al), (Co,Cr), Ni, Mg) at the 16d site is known to increase the average Mn-oxidation state, enabling the compound to be more tolerant to JahnTeller distortion, and an improved cathodic performance is observed. [5][6][7][8][9][10][11][12][13][14][15][16][17] The latter is also ascribed to the stronger M-O (M~Co, Cr, Al) bond strength compared to that of the Mn-O bond in the spinel structure.…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] The partial substitution of Mn as Li(M,Mn) 2 O 4 , (M~Li, Co, Cr, Al, (Co,Al), (Co,Cr), Ni, Mg) at the 16d site is known to increase the average Mn-oxidation state, enabling the compound to be more tolerant to JahnTeller distortion, and an improved cathodic performance is observed. [5][6][7][8][9][10][11][12][13][14][15][16][17] The latter is also ascribed to the stronger M-O (M~Co, Cr, Al) bond strength compared to that of the Mn-O bond in the spinel structure. 5,[10][11][12][13][14] The observed reduction in the initial charge-discharge capacity proportional to the amount of the substituent M leads to the conclusion that the Mn 31 ions in the lattice are replaced and the M ion is electrochemically inactive in the voltage range of operation, 3.5-4.3 V vs. Li.…”

Section: Introductionmentioning

confidence: 99%

“…5,[10][11][12][13][14] The main reasons for the capacity fading in LiMn 2 O 4 -type cathodes were ascribed to structural change and Mn dissolution on cycling the cells especially at high temperatures. [3][4][5][7][8][9][16][17][18][19][20][21] The increased impedance contribution of the LiMn 2 O 4 electrode with cycling was also correlated with the observed capacity fading in spinel compounds. 22,23 However, there are observations that the minor change in impedance of the electrode on cycling cannot account for the observed capacity fading and Premanand et al 24 concluded that the main cause is the structural change and associated active material dissolution in the electrolyte.…”

Section: Introductionmentioning

confidence: 99%

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Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

2002

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Pristine and substituted spinels, Li(M 1/6 Mn 11/6 )O 4 (M~Co 1/6 , Co 1/12 Al 1/12 ) were prepared and their cathodic performance up to 80 cycles at ambient temperature and at 50 uC and the Li ion kinetic parameters obtained by galvanostatic intermittent titration technique (GITT) at ambient temperature and 50 uC and electrochemical impedance spectroscopy (EIS) at ambient temperature up to 80 cycles were compared to understand the improved performance observed for the doped spinels. The apparent Li diffusion coefficient (D Li ) obtained from GITT in the voltage range of operation of the cell (3.5-4.3 V vs. Li) at ambient temperature and 50 uC is in the range 1 6 10 29 -10 210 cm 2 s 21 for M~Mn, Co and (Co,Al). The D Li vs. voltage plots show indication of suppression of two-phase formation in doped spinels. Distinct changes in the EIS-derived parameters and the D Li values in the compounds with M~Co, (Co,Al) as compared to LiMn 2 O 4 lead to the conclusion that the observed cycling stability in the doped spinels is contributed by the Li ion kinetics in addition to the suppression of the structural changes and associated material dissolution.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

2002

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“…Some researchers [83][84][85][86][87][88] showed that single-ion doping can improve the cycling stability of the spinel with reduced capacity because the dopants are not electrochemically active and do not contribute to the capacity, but this is inconsistent with the following example which gave higher capacity, but not so good cycle performance.…”

Section: Single-ion Dopingmentioning

confidence: 99%

Preparation and Doping Mode of Doped LiMn2O4 for Li-Ion Batteries

et al. 2013

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Spinel LiMn 2 O 4 is an appealing candidate cathode material for Li-ion rechargeable batteries, but it suffers from severe capacity fading, especially at higher temperature (55 °C) during discharging/charging. In recent years, many attempts have been made to synthesize modified LiMn 2 O 4 . This paper reviews the recent research on the preparation and doping modes of doped LiMn 2 O 4 for modifying the LiMn 2 O 4. We firstly compared preparation methods for doped spinel LiMn 2 O 4 , such as solid state reactions and solution synthetic methods. Then we mainly discuss doping modes reported in recent years, such as bulk doping, surface doping and combined doping. A comparison of different doping modes is also provided. The research shows that the multiple-ion doping and combined doping modes of LiMn 2 O 4 used in Li-ion battery are excellent for improving different aspects of the electrochemical performance which holds great promise in the future. From this paper, we also can see that spinel LiMnO 4 as an attractive candidate cathode material for Li-ion batteries.

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“…Spinel LiMn 2 O 4 is one of the most attractive cathode materials in the field of Li-ion batteries because of its high output voltage (4 V), low cost, abundance in nature, environmentally benign, and high safety [4][5][6][7][8][9][10]. However, it is well known to suffer from the structural transition from cubic to tetrahedron caused by Jahn-Teller (J-T) distortion when the average Mn-ion valency falls below 3.5, namely, when the LiMn 2 O 4 electrodes are cycled below 3 V, which leads to severe capacity fading during prolonged cycles [11][12][13] , have been explored to substitute partial Mn 3+ ions to increase the average valence of Mn ions and also limit the cyclic voltage in the range of 3.5-4.4 V, resulting in better cyclic performance compared to pristine LiMn 2 O 4 [14][15][16][17][18]. Shi et al [18] reported that LiFe 0.2 Mn 1.8 O 4 exhibited a discharge capacity of 122 mA h g −1 at 1 C (1 C = 148 mA g −1 ) and the capacity retention reached 88% after 500 cycles.…”

Section: Introductionmentioning

confidence: 99%

Spinel LiMn2−x Si x O4 (x < 1) through Si4+ substitution as a potential cathode material for lithium-ion batteries

et al. 2016

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Spinel LiMn2−xSixO4 (x< 1, through substituting Mn 4+ with Si 4+ in cubic spinel LiMn2O4) was synthesized successfully by a facile sol-gel method. The as-prepared LiMn2−xSixO4 consisted of pores with large size distribution range from a few nanometers to over 200 nm and possessed specific surface area of 8.76 m 2 g −1 . Results of X-ray powder diffraction and X-ray photoelectron spectroscopy confirmed that Si atoms entered the host lattice. As a cathode material for rechargeable lithium-ion batteries, spinel LiMn2−xSixO4 exhibited excellent structural reversibility and integrity during the charging-discharging process. The result indicated that substitution of Mn 4+ by Si 4+ in spinel LiMn2O4 material effectively alleviated the phase transition caused by Jahn-Teller effect. The initial discharge capacity of the as-prepared spinel LiMn2−xSixO4 was 147 mA h g −1 over the voltage range of 1.5-4.8 V. However, after 51 cycles, the specific capacity was 88 mA h g −1 with capacity retention of 60 %. More work is needed to understand the effects of substituting Mn 4+ by Si 4+ and to improve the cyclic stability.

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The elevated temperature performance of the LiMn2O4/C system: failure and solutions

Cited by 287 publications

References 37 publications

Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

Li ion kinetic studies on spinel cathodes, Li(M1/6Mn11/6)O4 (M = Mn, Co, CoAl) by GITT and EIS

Preparation and Doping Mode of Doped LiMn2O4 for Li-Ion Batteries

Spinel LiMn2−x Si x O4 (x < 1) through Si4+ substitution as a potential cathode material for lithium-ion batteries

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