Overcharging manganese oxides: Extracting lithium beyond Mn4+

Armstrong, A. Robert; Robertson, Alastair D.; Bruce, Peter G.

doi:10.1016/j.jpowsour.2005.03.104

Cited by 134 publications

(120 citation statements)

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“…Nevertheless, several publications have appeared with different procedures for activation of Li 2 MnO 3 and with varying capacity values. [5][6][7][8][9][10][11][12][13][14] The initial discharge capacity values are generally high for the activated phases of Li 2 MnO 3 , but cycling instability is observed in all reports. In order to enhance the cycling stability, composites of Li 2 MnO 3 with other layered lithiated transition metal oxides such as LiCoO 2 are studied.…”

mentioning

confidence: 99%

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Penki

Duraisamy

Kishore

et al. 2016

J. Electrochem. Soc.

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A porous layered composite of Li 2 MnO 3 and LiMn 1/3 Ni 1/3 Fe 1/3 O 2 (composition: Li 1.2 Mn 0.53 Ni 0.13 Fe 0.13 O 2 ) is prepared by reverse microemulsion method employing tri-block co-polymer, F068 as a soft-polymer template. The Co-free composite is studied as a cathode material for Li-ion battery. Several samples are prepared by heating the precursor in the temperature range between 500 and 900 • C. The N 2 adsorption/desorption studies reveal that the product samples possess mesoporosity with broadly distributed pores around 15-50 nm diameter. Pore volume and surface area decrease by increasing the temperature of preparation. Charge-discharge, cycling and rate capability are investigated. The discharge capacity of the sample prepared at 900 • C is about 170 mAh g −1 at a specific current of 25 mA g −1 with a good cycling stability. A value of 140 mAh g −1 is obtained at the end of 50 charge-discharge cycles. Discharge capacity of 91 mAh g −1 is obtained at a specific current of 206 mA g −1 . A high rate capacity of the composite is attributed to its porous nature. Research activities on lithium-ion batteries have increased in the recent past because of their attractive energy density. [1][2][3] In an extended range of applications, they are successful in small sizes at present and anticipated to be useful in large sizes for applications such as electric vehicles. Although the energy density of the present Li-ion batteries is the greatest among rechargeable batteries, future requirements such as electric vehicle applications require still greater energy density. The next generation Li-ion batteries, thus, need novel electrode materials which can provide greater discharge capacity than the present materials. Compounds with a high atomic ratio of extractable lithium to transition metal are expected to provide high discharge capacity values. Li 2 MnO 3 belongs to this category of materials.4 Li 2 MnO 3 is a layered oxide similar to LiCoO 2 and its formula can also be presented as Li (Li 0.33 was reported at a specific current of 30 mA g −1 in the potential range between 1.5 and 4.8 V. 33,34 In addition to the high discharge capacity, an electrode material needs to possess high rate capability for the purpose of fast charge or/and discharge. Porous materials are expected to possess high rate capability because the electrolyte can creep into particles and enhance the contact area. 35 As a result, the material can withstand an enhanced specific current during charge-discharge cycling. Furthermore, the electrode material can tolerate volume expansion and contraction that may occur during charge-discharge processes. To the best of authors' knowledge, there are only few reports available on the synthesis of porous composites of Li 2 MnO 3 . A porous composite of Li 2 MnO 3 with nanoplate morphology was prepared via colloidal crystal template of poly(methyl methacrylate) beads. The porous composite was better in electrochemical properties in relation to the nonporous composite. 36,37 Investigations on high capa...

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confidence: 99%

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Penki

Duraisamy

Kishore

et al. 2016

J. Electrochem. Soc.

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“…The symmetry of the crystal lattice was approximated to be trigonal (R-3m) [13,14,15,16]. The (020) reflection peak at 21 o 2θ was observed, which is characteristic of the integrated monoclinic Li 2 MnO 3 -like component (C2/ m) [17,18,19]. The peak at 36 o indicated the spinelphase Li x Mn 2 O 4 (010), which didn't show in the pristine substituted materials, and increased with increasing in the amount of fluorine.…”

Section: Methodsmentioning

confidence: 99%

Electrochemical Performances of the Fluorine-Substituted on the 0.3Li₂MnO₃·0.7LiMn_0.60Ni_0.25Co_0.15O₂Cathode Material

Kim¹,

Jin²,

Park³

et al. 2014

Journal of Electrochemical Science and Technology

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“…The ultimate products of the oxidation of carbonate solvents are CO 2 and H 2 O, and organic acids (H + ) are the possible intermediate of the solvent oxidization (Armstrong et al, 2005 (Liu and Manthiram, 2009), and solid electrolyte (Li et al, 2013) shows very effective in suppressing the metal dissolution, this strategy is certainly applicable to the gassing reduction. Lithium bis(oxalato)borate (LiBOB) is very effective in suppressing metal dissolution, however, it is oxidized to generate CO 2 at high potentials.…”

Section: Spinel Cathode Materialsmentioning

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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Overcharging manganese oxides: Extracting lithium beyond Mn4+

Cited by 134 publications

References 23 publications

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Electrochemical Performances of the Fluorine-Substituted on the 0.3Li₂MnO₃·0.7LiMn_0.60Ni_0.25Co_0.15O₂Cathode Material

Insight into the Gassing Problem of Li-ion Battery

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Overcharging manganese oxides: Extracting lithium beyond Mn4+

Cited by 134 publications

References 23 publications

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Composite of Li-Rich Mn, Ni and Fe Oxides as Positive Electrode Materials for Li-Ion Battery

Electrochemical Performances of the Fluorine-Substituted on the 0.3Li2MnO3·0.7LiMn0.60Ni0.25Co0.15O2Cathode Material

Insight into the Gassing Problem of Li-ion Battery

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Electrochemical Performances of the Fluorine-Substituted on the 0.3Li₂MnO₃·0.7LiMn_0.60Ni_0.25Co_0.15O₂Cathode Material