Microstrain and Capacity Fade in Spinel Manganese Oxides

Shin, Youngjoon; Manthiram, Arumugam

doi:10.1149/1.1450063

Cited by 94 publications

(74 citation statements)

References 18 publications

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“…The peak broadening has recently been attributed by our group to the development of microstrain in the LiMn 2 O 4 lattice, which is suppressed by cationic substitutions. 22 It has been reported before by Amatucci et al 15 that the crystallinity decreases proportionately with the percent of capacity loss. The surface/chemical modification of LiMn 2 O 4 appears to suppress the attack by the acidic species present in the electrolyte as well as the occurrence of Jahn-Teller distortion on the surface 9 and thereby leads to better structural integrity with low microstrain and good capacity retention during cycling.…”

Section: Resultsmentioning

confidence: 84%

Surface/Chemically Modified LiMn[sub 2]O[sub 4] Cathodes for Lithium-Ion Batteries

Kannan

Manthiram

2002

Electrochem. Solid-State Lett.

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146

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LiMn 2 O 4 spinel oxide has been surface/chemically modified with Li x CoO 2 , LiNi 0.5 Co 0.5 O 2 , Al 2 O 3 , and MgO using a chemical processing procedure followed by heat-treatment at 300-800°C. The surface/chemically modified samples show much better capacity retention at both 25 and 60°C than does the unmodified LiMn 2 O 4 ͑41% fade in 100 cycles at 60°C͒. Among the various compositions investigated, the LiNi 0.5 Co 0.5 O 2 -modified sample shows superior capacity retention with only 2.8% fade in 100 cycles at 60°C with around 110 mAh/g. The Al 2 O 3 -modified sample shows a higher capacity of 130 mAh/g, but with a faster fade ͑16% in 100 cycles at 60°C͒. The Li 0.75 CoO 2 -modified sample shows the best combination of capacity ͑124 mAh/g͒ and retention ͑8% fade in 100 cycles at 60°C͒. The modified samples also exhibit better capacity retention after aging at 55°C at 60-70% depth of discharge. is found to show excellent capacity retention with a capacity fade of Ͻ0.03% per cycle over 100 cycles at 60°C and C/2 rate. ExperimentalThe surface/chemical modification was accomplished by treating a commercially available LiMn 2 O 4 powder ͑Carus Chemical Company͒ with various amounts of the precursor solutions of Li x CoO 2 , LiCo 0.5 Ni 0.5 O 2 , Al 2 O 3 , or MgO through a chemical process so that the amount of the modifying material in the final product is 3-5 wt %.The modification with Li x CoO 2 and LiCo 0.5 Ni 0.5 O 2 involved a dissolution of the carbonates or acetates of the precursor metal ions in glacial acetic acid, refluxion of the mixture for about an hour, dispersion of the LiMn 2 O 4 spinel oxide in the precursor solution, evaporation of the solvent, and decomposition of the resultant product at around 400°C, followed by firing at 850°C in a flowing oxygen atmosphere for 12 h.The modifications with Al 2 O 3 and MgO involved the dispersion of the LiMn 2 O 4 spinel oxide in an aqueous solution of aluminum or magnesium nitrate, precipitation of hydrous aluminum or magnesium oxide over LiMn 2 O 4 particles through the addition of ammonium hydroxide, and heating the resultant product at 300 and 600°C, respectively, in air for 4 h.Cathodes were fabricated with the surface/chemically modified and unmodified LiMn 2 O 4 powder, Denka black carbon, and polytetrafluoroethylene ͑PTFE͒ binder in a weight ratio of 75:20:5. The electrochemical performances were evaluated with CR2032 coin cells assembled with the cathodes thus fabricated, metallic lithium anodes, polyethylene separators, and 1 M LiPF 6 in ethylene carbonate ͑EC͒ and diethyl carbonate ͑DEC͒ electrolyte between 3.5 and 4.3 V. Aging experiments were carried out as follows. After the first two cycles at a current density of 0.5 mA/cm 2 ͑C/2 rate͒, the coin cells were discharged to DOD ͑depth of discharge͒ values of 60 and 70% in the third cycle at room temperature. The cells were then subjected to aging at a constant temperature of 55°C for 100 h and the remaining capacity was determined by discharging the aged cells at room temperature to a cutoff vo...

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Section: Resultsmentioning

confidence: 84%

Surface/Chemically Modified LiMn[sub 2]O[sub 4] Cathodes for Lithium-Ion Batteries

Kannan

Manthiram

2002

Electrochem. Solid-State Lett.

Self Cite

146

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“…The stresses can arise from anisotropic lattice expansion and contraction upon Li + extraction/insertion, which cause volume variation of the grains. [80] The individual grains in a sintered secondary particle are physically constrained by their neighboring primary particles and stress arising from the anisotropic volume change can cause particle fracture in long term cycle. The differential expansion within a single grain can also contribute to microstrain because a Li + concentration gradient always exists in a primary particle during charge-discharge process.…”

Section: Microstrain and Crack Of Primary Particlesmentioning

confidence: 99%

Nickel‐Rich Layered Lithium Transition‐Metal Oxide for High‐Energy Lithium‐Ion Batteries

et al. 2015

Angew Chem Int Ed

1,611

1,186

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High energy-density lithium-ion batteries are in demand for portable electronic devices and electrical vehicles. Since the energy density of the batteries relies heavily on the cathode material used, major research efforts have been made to develop alternative cathode materials with a higher degree of lithium utilization and specific energy density. In particular, layered, Ni-rich, lithium transition-metal oxides can deliver higher capacity at lower cost than the conventional LiCoO2 . However, for these Ni-rich compounds there are still several problems associated with their cycle life, thermal stability, and safety. Herein the performance enhancement of Ni-rich cathode materials through structure tuning or interface engineering is summarized. The underlying mechanisms and remaining challenges will also be discussed.

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“…Elevated temperature effects on spinel dissolution.-Many investigations 8,14,[18][19][20][21][22][23] have shown that the dissolution of Mn was accelerated at elevated temperatures leading to a faster capacity fading. Plots of the cyclic voltammogram of three spinel LiMn 2 O 4 disk electrodes in the beaker cell cycled between 3.0 and 4.5 V with 10 mV/s, 500 rpm, and 1 M LiPF 6 ϩ EC/DMC ͑1:1͒ electrolyte, at 30, 45, and 58°C are shown in Fig.…”

Section: Mnmentioning

confidence: 99%

“…14,15 Although many possible factors have been proposed to contribute to the capacity fading of the spinel LiMn 2 O 4 electrode, most of the evidence reported so far points to manganese dissolution at the top of charge as the major reason for the capacity fading. It is essential to investigate the dissolution behavior of the spinel electrode in order to improve the capacity fading of the spinel materials.…”

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

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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...

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Microstrain and Capacity Fade in Spinel Manganese Oxides

Cited by 94 publications

References 18 publications

Surface/Chemically Modified LiMn[sub 2]O[sub 4] Cathodes for Lithium-Ion Batteries

Surface/Chemically Modified LiMn[sub 2]O[sub 4] Cathodes for Lithium-Ion Batteries

Nickel‐Rich Layered Lithium Transition‐Metal Oxide for High‐Energy Lithium‐Ion Batteries

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

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