Mechanisms of manganese spinels dissolution and capacity fade at high temperature

Aoshima, Takayuki; Okahara, Kenji; Kiyohara, Chikara; Shizuka, Kenji

doi:10.1016/s0378-7753(01)00551-1

Cited by 160 publications

(146 citation statements)

References 4 publications

Supporting

Mentioning

142

Contrasting

Order By: Relevance

“…In addition to the co-existence of two cubic phases in the 4 V region, it is known that the capacity fade in LiMn 2 O 4 occurs mainly by the formation of lithiated spinel, Li 2 Mn 2 O 4 , at the surface of the electrode towards the end of discharge and the dissolution of Mn in the electrolyte by the disproportionation reaction, 2Mn 31 (s) A Mn 41 (s) 1 Mn 21 (sln). [1][2][3]7,19,20 The CV profile at 50 uC does not show any additional peaks, but the anodic peak positions around 4.1 V of the undoped and doped spinels shift slightly to lower voltage and become more prominent as compared to the values at ambient temperature. In addition, for LiMn 2 O 4 there is a decrease in the peak intensity.…”

mentioning

confidence: 93%

“…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%

“…However, LiMn 2 O 4 at 50 uC shows a slightly higher voltage at the end-ofcharge compared to the profile at ambient temperature. This could be due to the presence of degradation products (such as Li 2 MnO 3 , l-MnO 2 ) as observed by others on cycling LiMn 2 O 4 at elevated temperatures [7][8][9]19,31 and which can bring about a change in the equilibrium potential. Further, such a change in voltage profile can also be possible by the conversion of the high voltage, coexisting two-phase region, to a more stable single-phase on cycling the cell at elevated temperatures as reported by Amatucci et al 2 and Xia et al 3 The continuous increase in cell voltage at 50 uC compared to the flat plateau at ambient temperature (more clearly seen in the equilibrium (steady-state) cell voltage (E s ) vs. x plot discussed later) on charging LiMn 2 O 4 is also in support to this argument.…”

mentioning

confidence: 99%

See 2 more Smart Citations

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

2002

View full text Add to dashboard Cite

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.

show abstract

mentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 1 more Smart Citation

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

2002

View full text Add to dashboard Cite

show abstract

“…1 However, capacity fading during charge/discharge cycling is a problem for the spinel, particularly at elevated temperatures. Several factors have been proposed to contribute to the capacity fading such as ͑i͒ the electrochemical reaction with the electrolyte at high voltage, 2,3 (ii) manganese dissolution into the electrolyte due to acid attack and a disproportion reaction at the particle surface [4][5][6][7] ͗2Mn ͑solid )3ϩ → Mn ͑solid)…”

mentioning

confidence: 99%

Study of Mn Dissolution from LiMn[sub 2]O[sub 4] Spinel Electrodes Using Rotating Ring-Disk Collection Experiments

Wang¹,

Ou²,

Striebel³

et al. 2003

J. Electrochem. Soc.

106

View full text Add to dashboard Cite

The goal of this research was to measure Mn dissolution from a thin porous spinel LiMn 2 O 4 electrode by rotating ring-disk collection experiments. The amount of Mn dissolution from the spinel LiMn 2 O 4 electrode under various conditions was detected by potential step chronoamperometry. The concentration of dissolved Mn was found to increase with increasing cycle numbers and elevated temperature. The dissolved Mn was not dependent on disk rotation speed, which indicated that the Mn dissolution from the disk was under reaction control. The in situ monitoring of Mn dissolution from the spinel was carried out under various conditions. The ring currents exhibited maxima corresponding to the end-of-charge ͑EOC͒ and end-of-discharge ͑EOD͒, with the largest peak at EOC. The results suggest that the dissolution of Mn from spinel LiMn 2 O 4 occurs during charge/discharge cycling, especially in a charged state ͑at Ͼ4.1 V͒ and in a discharged state ͑at Ͻ3.1 V͒. The largest peak at EOC demonstrated that Mn dissolution took place mainly at the top of charge. At elevated temperatures, the ring cathodic currents were larger due to the increase of Mn dissolution rate. The rapid progress in development and widespread use of portable electronic devices have led to a great demand for portable, lightweight power sources. Lithium-ion technology has met these requirements, and has been used commercially for over ten years because it offers high energy and power density, high voltage, longlife, and reliability. The performance of lithium-ion batteries is to a large degree determined by the cathode material. There have been many studies of the cathode materials during the last decade. Although LiCoO 2 has been widely used as the cathode material in the commercial lithium-ion batteries for many years, the lithium manganese oxide spinel LiMn 2 O 4 is a promising alternative cathode material in the future because of its high voltage, low cost, and environmental friendliness. These attractive characteristics make spinel LiMn 2 O 4 a good candidate for large-scale Li-ion batteries for electric vehicle ͑EV͒ and hybrid electric vehicle ͑HEV͒ applications.1 However, capacity fading during charge/discharge cycling is a problem for the spinel, particularly at elevated temperatures. Several factors have been proposed to contribute to the capacity fading such as ͑i͒ the electrochemical reaction with the electrolyte at high voltage, 2,3 (ii) manganese dissolution into the electrolyte due to acid attack and a disproportion reaction at the particle surfaceinstability of the two-phase structure in the charged state leading to the loss of MnO and dissolution of Mn to a more stable single-phase structure, 4,8,9 (iv) formation of tetragonal Li 2 Mn 2 O 4 on the surface of the spinel and the associated Jahn-Teller distortion at the end of discharge, especially under high current density, nonequilibrium conditions, 5,10,11 (v) formation of oxygen-deficient spinels, 12 (vi) cation mixing between the lithium and manganese sites in the spinel lattice, 13 an...

show abstract

“…[1][2][3] Even if it has been extensively studied as a potential electrode, there are still several challenges of LiMn2O4 material for lithium secondary battery such as capacity fading, manganese dissolution at elevated temperature, and poor high-rate capability. Many researchers have made tremendous efforts to improve the performance of LiMn 2 O 4 and found that these drawbacks were mainly attributed to two factors: (i) the acid-induced dissolution of manganese ion 4,5 and (ii) JahnTeller effect of the high spin Mn 3+ . 6,7 The addition of different metal ion to LiMn2O4 might be expected to suppress the JahnTeller effect by the increase in the oxidation state of Mn and stabilize the cubic structure.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Electrochemical Properties of Surface Modified LiMn₂O₄by Li-Fe Composites for Rechargeable Lithium Ion Batteries

Shi¹,

Liang³

et al. 2010

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

The surface modified LiMn2O4 materials with Li-Fe composites were prepared by a sol-gel method to improve the electrochemical performance of LiMn2O4 and were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and transmission electron microscopy (TEM)-EDS. XRD results indicate that all the samples (modified and pristine samples) have cubic spinel structures, and XRD, XPS, and TEM-EDS data reveal the formation of Li(LixFexMn2-2x)O4 solid solution on the surface of particles. For the electrochemical properties, the modified material demonstrated dramatically enhanced reversibility and stability even at elevated temperature. These improvements are attributed to the formation of the solid solution, and thus-formed solid solution phase on the surface of LiMn2O4 particle reduces the dissolution of Mn ion and suppresses the Jahn-Teller effect.

show abstract

Mechanisms of manganese spinels dissolution and capacity fade at high temperature

Cited by 160 publications

References 4 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

Study of Mn Dissolution from LiMn[sub 2]O[sub 4] Spinel Electrodes Using Rotating Ring-Disk Collection Experiments

Enhanced Electrochemical Properties of Surface Modified LiMn₂O₄by Li-Fe Composites for Rechargeable Lithium Ion Batteries

Contact Info

Product

Resources

About

Mechanisms of manganese spinels dissolution and capacity fade at high temperature

Cited by 160 publications

References 4 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

Study of Mn Dissolution from LiMn[sub 2]O[sub 4] Spinel Electrodes Using Rotating Ring-Disk Collection Experiments

Enhanced Electrochemical Properties of Surface Modified LiMn2O4by Li-Fe Composites for Rechargeable Lithium Ion Batteries

Contact Info

Product

Resources

About

Enhanced Electrochemical Properties of Surface Modified LiMn₂O₄by Li-Fe Composites for Rechargeable Lithium Ion Batteries