Capacity Fading of Graphite Electrodes Due to the Deposition of Manganese Ions on Them in Li-Ion Batteries

Tsunekawa, Hajime; Tanimoto, Akira; Marubayashi, Ryoji; Fujita, Miho; Kifune, Koichi; Sano, Mitsuru

doi:10.1149/1.1502686

Cited by 129 publications

(126 citation statements)

References 22 publications

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“…22,28,33 Formation of different metal fluorides and carbonates including LiF and Li 2 CO 3 have been reported on the SEI formed on the negative electrode with transition metal present in the electrolyte. In this work, we also identified Li 2 CO 3 as a component in the surface layer of the graphite electrode of the cell with transition metal salts added in the electrolyte.…”

Section: Resultsmentioning

confidence: 99%

“…18,25,26 Transition metal ions resulting from dissolution diffuse across the separator and are reduced on the negative electrode. 4,16,19,21,[27][28][29][30][31][32][33] Since the growth of the SEI layer on negative electrodes is one of the major factors leading to capacity fade in Li-ion batteries, it is important to understand the effect of metal dissolution on the properties of the SEI layer. 21,22,[34][35][36][37][38][39][40][41] Understanding the changes occurring in the electrodes and the associated effect on the electrochemical performance of the cell is important in assessing the long-term behavior of these materials.…”

Section: 7-14mentioning

confidence: 99%

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Effects of Dissolved Transition Metals on the Electrochemical Performance and SEI Growth in Lithium-Ion Batteries

Joshi

Eom

Yushin

et al. 2014

J. Electrochem. Soc.

181

161

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Transition metal dissolution is one of the major causes of capacity and power fade in lithium-ion batteries employing transition metal oxides in the positive electrode. Accelerated testing was accomplished by introducing transition-metal salts in the electrolyte in order to study the effects of dissolution on performance. It is shown that metal dissolution causes a reduction in capacity and cycle stability in full cells. The SEI layer resistance in the negative electrode of full cells increases with increasing concentration of transition metal salts. The growth of the SEI layer is non-uniform and is believed to be caused by the reduction of transition metal species in the negative electrode leading to an increase in inorganic component of the SEI layer. Consumption of fossil fuels in the transportation sector is one of the leading causes of greenhouse gas emissions (GHG).1 Efforts to develop cleaner and more efficient alternatives to the internal combustion engine running on petroleum fuels, such as fuel cells and batteries, are on the rise to mitigate this problem. Rechargeable lithium-ion (Li-ion) batteries offer high energy and power densities, good cyclic stability, and low rates of self-discharge. These characteristics are essential for applications in hybrid electric vehicles (HEV), plug-in hybrid vehicles (PHEV), and electric vehicles (EV). Dissolution of transition metals from the positive electrode is a concern for lithium-ion batteries, and manganese dissolution is a major reason for capacity fade in spinel electrodes, including LiMn 2 O 4 . 15Although less susceptible than spinel, metal dissolution does occur in NCM electrodes and has been implicated in a rise in impedance and capacity fade with cycling. 4,16 Two main routes by which capacity fading may occur due to dissolution are (i) structural changes to the positive electrode and leading to reduced insertion capacity and (ii) accelerated growth of the SEI layer at the negative electrode and the resulting irreversible Li consumption. 15,[17][18][19][20][21][22] Capacity fade due to the structural changes occurring in the positive electrode during partial dissolution is more likely in spinel electrodes, where the extent of dissolution is high, or at high potentials (overcharge). This large degree of dissolution in spinels may cause shrinkage of the active material, which decreased the effective transport properties and kinetics of the electrode.20,23 The extent of dissolution in different positive electrode materials was compared by Choi and Manthiram, 18 and amount of Mn dissolution is 16 times greater in LiMn 2 O 4 compared to NCM electrodes. They also reported that structural stability is directly related to the extent of dissolution in electrodes. 18Dissolution may also cause a decrease in cell capacity by increased growth and breakdown of the SEI layer 21,22 on the negative electrode. Although dissolution has been studied extensively in spinel electrode materials and its negative effects on cell capacity have been wellestablished, how dissoluti...

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Section: Resultsmentioning

confidence: 99%

Section: 7-14mentioning

confidence: 99%

Effects of Dissolved Transition Metals on the Electrochemical Performance and SEI Growth in Lithium-Ion Batteries

Joshi

Eom

Yushin

et al. 2014

J. Electrochem. Soc.

181

161

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“…[20][21][22][23] This last source, especially the dissolution of Mn and its deposition in the negative electrode SEI, has been shown to be particularly detrimental to cell performance. [24][25][26] All steps of the dissolution, migration, and incorporation process involving the TM ions are insufficiently understood, and even the state of TMs in the SEI continues to be the subject of controversy (see Refs. 27-29 for a review).…”

mentioning

confidence: 99%

Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells

Gilbert

Shkrob

Abraham

2017

J. Electrochem. Soc.

420

513

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Continuous operation of full cells with layered transition metal (TM) oxide positive electrodes (NCM523) leads to dissolution of TM ions and their migration and incorporation into the solid electrolyte interphase (SEI) of the graphite-based negative electrode. These processes correlate with cell capacity fade and accelerate markedly as the upper cutoff voltage (UCV) exceeds 4.30 V. At voltages ≥4.4 V there is enhanced fracture of the oxide during cycling that creates new surfaces and causes increased solvent oxidation and TM dissolution. Despite this deterioration, cell capacity fade still mainly results from lithium loss in the negative electrode SEI. Among TMs, Mn content in the SEI shows a better correlation with cell capacity loss than Co and Ni contents. As Mn ions become incorporated into the SEI, the kinetics of lithium trapping change from power to linear at the higher UCVs, indicating a large effect of these ions on SEI growth and implicating (electro)catalytic reactions. We estimate that each Mn II ion deposited in the SEI causes trapping of ∼10 2 additional Li + ions thereby hastening the depletion of cyclable lithium ions. Using these results, we sketch a mechanism for cell capacity fade, emphasizing the conceptual picture over the chemical detail. Increasing the energy and power density of Li-ion batteries (LIBs) for transportation applications is desirable for extending driving range and for providing the burst of power required for vehicle acceleration.1-3 Layered transition metal (TM) oxides containing Co, Mn, and Ni are promising high-energy electrode materials, as they exhibit theoretical oxide-specific capacities >200 mAh/g and can be cycled to potentials exceeding 4.50 V vs. Li/Li + . 4,5 However, the performance deterioration of full cells, in which these oxides are paired with a graphite (Gr) negative electrode, increases markedly at potentials exceeding 4.30 V, limiting their wider use as high-energy cathode materials.6,7 Therefore, it is imperative to examine the causes for their performance loss at high voltages. In this study we aim at understanding both the phenomenology and mechanism of capacity loss; mitigation of this loss will be the focus of future articles.Several possible causes for cell performance degradation have been identified over the years. These causes include, but are not limited to (i) TM oxide structure changes leading to voltage fade, 8 (ii) buildup of electrode surface films, especially the solid-electrolyte interphases (SEIs) 9,10 at the negative electrode, leading to Li + inventory depletion and/or impedance rise, 11-13 (iii) decomposition of the electrolyte, [14][15][16] (iv) pitting corrosion of aluminum current collectors, 17-19 (v) binder destabilization leading to delamination of electrode coatings, and (vi) dissolution of electrode-active materials. [20][21][22][23] This last source, especially the dissolution of Mn and its deposition in the negative electrode SEI, has been shown to be particularly detrimental to cell performance. [24][25][26] All steps o...

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“…Spinel-type lithium manganese oxide (LiMn 2 O 4 ) is one of the most promising cathode materials for large-format lithium ion batteries for electric vehicles (EV) due to its cost-effectiveness, facile production, high discharge voltage plateau (∼4.0 V vs. Li/Li + ) and environmental benignity compared to other cathode materials [1][2][3]. Moreover, the LiMn 2 O 4 battery can deliver much higher energy density more than 200Wh/kg in order to meet the requirement of EV long driving ranges when compared to the corresponding lithium ion batteries (150Wh/kg).…”

Section: Introductionmentioning

confidence: 99%

“…These features, especially, along with their low cost and environmental benignity, render them an attractive substitute for lead-acid batteries in battery-operated motor or EV. However, LiMn 2 O 4 based battery suffers from poor cyclic capability, especially at elevated temperatures (above 55 • C) [1][2][3][4][5][6][7][8][9][10]. This drawback is mainly related to continuous growth of cell impedance and Mn dissolution caused by the harmful components (LiF and HF) from the decomposing reaction of the LiPF 6 salt at elevated temperatures.…”

Section: Introductionmentioning

confidence: 99%

A single-ion gel polymer electrolyte system for improving cycle performance of LiMn2O4 battery at elevated temperatures

Qin

Liu

Ding

et al. 2014

Electrochimica Acta

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a b s t r a c tThe LiMn 2 O 4 based lithium batteries using commercially available electrolytes suffer from poor cycling performance at elevated temperatures (above 55• C). This is mainly caused by the Mn dissolution generated from HF thermally decomposed from the LiPF 6 salt at elevated temperatures. In this paper, a single-ion gel polymer electrolyte (polymeric lithium tartaric acid borate @ poly(vinylidene fluoride-cohexafluoropropylene) was explored for improving the cycling performance of the LiMn 2 O 4 based lithium battery at elevated temperatures owing to superior thermal stability and comparable ionic conductivity. It was manifested that the Li/LiMn 2 O 4 cells using this single-ion gel polymer electrolyte showed stable charge/discharge voltage profiles, preferable rate capability and excellent cycling performance both at room temperature and elevated temperature of 55• C. The dissolution of metallic Mn in this electrolyte is significantly suppressed than that of LiPF 6 electrolyte. These superior performances could endow this single-ion gel polymer electrolyte a promising alternative to the conventional liquid electrolyte system in the LiMn 2 O 4 battery at elevated temperatures.

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Capacity Fading of Graphite Electrodes Due to the Deposition of Manganese Ions on Them in Li-Ion Batteries

Cited by 129 publications

References 22 publications

Effects of Dissolved Transition Metals on the Electrochemical Performance and SEI Growth in Lithium-Ion Batteries

Effects of Dissolved Transition Metals on the Electrochemical Performance and SEI Growth in Lithium-Ion Batteries

Transition Metal Dissolution, Ion Migration, Electrocatalytic Reduction and Capacity Loss in Lithium-Ion Full Cells

A single-ion gel polymer electrolyte system for improving cycle performance of LiMn2O4 battery at elevated temperatures

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