Study of Mn dissolution from LiMn2O4 spinel electrodes using in situ total reflection X-ray fluorescence analysis and fluorescence XAFS technique

Terada, Yasuko; Nishiwaki, Yoshinori; Nakai, Izumi; Nishikawa, Fumishige

doi:10.1016/s0378-7753(01)00741-8

Cited by 80 publications

(77 citation statements)

References 7 publications

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“…Therefore, the Mn dissolution was accelerated for higher cycle number. A similar dissolution tendency was reported by Terada et al 18 In Fig. 4, the rapid capacity fading initially is not caused only by the simple dissolution of Mn since the Mn dissolution rate is almost constant before 150 cycles.…”

Section: Mnsupporting

confidence: 88%

“…Recently, Terada et al monitored the concentration of Mn in an electrolyte solution during the electrochemical cycling by in situ methods using a combination of TXRF analysis and a capillary technique. 18 The rotating ring-disk electrode ͑RRDE͒ technique is another useful in situ technique to measure the Mn dissolution of the spinel LiMn 2 O 4 electrode. In this work, the Mn dissolution behavior of the spinel electrode has been first explored by the RRDE technique.…”

Section: 15mentioning

confidence: 99%

“…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%

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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.

109

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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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Section: Mnsupporting

confidence: 88%

Section: 15mentioning

confidence: 99%

Section: Mnmentioning

confidence: 99%

See 1 more Smart Citation

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.

109

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“…This finding reveals that the metal dissolution is also associated with the direct redox between the delithiated cathode material (for example, MnO 2 for LiMn 2 O 4 ) and electrolyte solvents. Comparison of the previous results (Terada et al, 2001;Lee et al, 2003) indicates an excellent corresponding correlation between the swelling-SOC chart and the metal dissolution-SOC chart, suggesting that the metal dissolution must be accompanied by the gas generation. Therefore, the strategies for suppressing the metal dissolution are also applicable to the reduction of gas generation.…”

Section: On Cathodesupporting

confidence: 51%

“…In addition to those staying in the electrolyte solution, the dissolved metal ions are also incorporated into the SEI of two electrodes by combining with the solvent decomposition molecular moieties on the electrodes (both the cathode and the anode) or being reduced into the metal on the anode, leading to a rise in the SEI resistance (Xu, 2014). It is interesting to note that the metal dissolution is highly dependent of the SOC, showing a dramatic increase as the SOC approaches the end of charging (Terada et al, 2001;Pieczonka et al, 2013). This finding reveals that the metal dissolution is also associated with the direct redox between the delithiated cathode material (for example, MnO 2 for LiMn 2 O 4 ) and electrolyte solvents.…”

Section: On Cathodementioning

confidence: 99%

Insight into the Gassing Problem of Li-ion Battery

Zhang

2014

Front. Energy Res.

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Gas generation (namely, the volume swelling of battery, or called the gassing) is a common phenomenon of the degradation of battery performance, which is generally a result of the electrolyte decomposition occurring during the entire lifespan of Li-ion batteries no matter whether the battery is in service or not. Abuse conditions such as overcharging and overheating make the gassing worse or even result in disastrous accidents. In overcharging, the gassing occurs mainly through the electrochemical oxidation of electrolyte solvents on the cathode with the Li + ions from the electrolyte being reduced into metallic Li on the anode. In overheating, the gassing takes place through not only the redox decomposition but also the chemical decomposition of the electrolyte solvents on both the anode and cathode besides the vapor expansion of volatile electrolyte solvents. In this opinion article, only the gas generation occurring under the normal operation and storage conditions will be addressed.Assuming that the Li-ion battery is well formed in manufacture and properly operated in service, the gas generation can be attributed to the chemical decomposition and redox decomposition of the electrolyte solvents on the anode and cathode. The chemical decomposition of dialkyl carbonate solvents produces ether and CO 2 , as described by Eq. 1, which can take place on both the anode and cathode. Resulting CO 2 can be reduced into CO in accompany with the consumption of Li + ions that are eventually originated from the cathode either by the chemical reduction (Eq. 2) or by the electrochemical reduction (Eq. 3) on the anode.Therefore, CO 2 and CO are often coexistent inside the battery. In particular, the chemical decomposition is increased with the temperature, and the redox decomposition is increased with the state-ofcharge (SOC) of battery. Chemical decomposition of the carbonate solvents is catalyzed by the anode, cathode, conducting carbon, and impurity particles, and lasts the entire lifespan of the Li-ion battery. Since a catalyst can be effectively deactivated by very small amounts of poisoning species, electrolyte additives appear to be very effective in suppressing the gas generation.For the gas generation caused by the redox decomposition of electrolyte solvents on two electrodes, Figure 1 shows that the swelling ratio of a graphite/LiCoO 2 cell remains nearly constant when the SOC is lower than 80%, however, dramatically increases as the SOC exceeds 80% (Lee et al., 2003). Potential-capacity profiles of the charging process indicate that the potential of the graphite anode is very flat at~0.25 V vs. Li/Li + , whereas that of the LiCoO 2 cathode linearly increases with the SOC (Zhang et al., 2006). This observation suggests that the gassing below 80% SOC can be attributed to the reduction of electrolyte solvents on the anode, and the increased gassing above 80% SOC to the oxidization of electrolyte solvents on the cathode. The redox-relative gas generation is closely associated with the anode and cathode materials, which...

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Inorganic Additives and Electrode Interface

Komaba

2009

Lithium Ion Rechargeable Batteries

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Study of Mn dissolution from LiMn2O4 spinel electrodes using in situ total reflection X-ray fluorescence analysis and fluorescence XAFS technique

Cited by 80 publications

References 7 publications

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

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

Insight into the Gassing Problem of Li-ion Battery

Inorganic Additives and Electrode Interface

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