Degradation of the solid electrolyte interphase induced by the deposition of manganese ions

Shin, Hosop; Park, Jong‐Hyun; Sastry, Ann Marie; Lü, Wei

doi:10.1016/j.jpowsour.2015.03.039

Cited by 90 publications

(71 citation statements)

References 44 publications

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“…This migration is, perhaps, the most problematic part of Leung's mechanism where further chemical insight is needed. Nevertheless, we remind the reader that the recent study of Shin et al 26 did suggest that most Mn becomes deposited relatively close to the graphite surface as opposed to the SEI surface, precisely in the manner envisioned in Figure 12. Another important consideration is that in some cycling experiments, 79 ca.…”

Section: -78mentioning

confidence: 51%

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

Gilbert

Shkrob

Abraham

2017

J. Electrochem. Soc.

419

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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Section: -78mentioning

confidence: 51%

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

Gilbert

Shkrob

Abraham

2017

J. Electrochem. Soc.

419

513

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“…3 Deposition of transition metal ions, which are dissolved from the cathode active materials at elevated temperatures, onto the anode/electrolyte interface also contributes significantly to the degradation of the SEI layer. [5][6][7] Degradation of the SEI layer results in SEI reformation and growth, during which cyclable lithium ions are additionally consumed due to further electrolyte reduction reactions. Thus, the degraded SEI layer cannot sustain its original properties, which affects the degradation of anode performance.…”

mentioning

confidence: 99%

Effects of Fluoroethylene Carbonate (FEC) on Anode and Cathode Interfaces at Elevated Temperatures

Shin

Park

Sastry³

et al. 2015

J. Electrochem. Soc.

Self Cite

132

106

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The use of electrolyte additives is one of the most effective and economical ways to improve battery performance by stabilizing the electrode/electrolyte interface. In this work, we identified that fluoroethylene carbonate (FEC), which is one of the important electrolyte additives, had different impacts on anode and cathode, by investigating a graphite anode and a LiMn 2 O 4 cathode through electrochemical analyses at room and elevated temperatures. In the anode side, the solid electrolyte interphase (SEI) layer derived from FEC exhibited a lower interfacial resistance and excellent thermal stability, showing excellent rate capability and improved cycle retention of cells. In contrast, poor cycling retention and a rapid increase in the interfacial resistance of the cathode were observed at elevated temperature. The poorer performance of the cathode in the FEC-containing cell at elevated temperature was attributed to the formation of a thicker surface layer and to increased Mn dissolution catalyzed by HF, which resulted from FEC dehydrofluorination initiated or accelerated by elevated temperature. Accordingly, it is suggested that the amount of FEC in a full cell must be optimized to minimize the adverse effects of FEC on cathode.It is well known that lithium-ion (Li-ion) batteries experience significant capacity fade during cycling or storage at elevated temperatures. However, the mechanisms responsible for the capacity fade at elevated temperatures are poorly understood because the capacity fade is caused by several interdependent factors. On anode side, most previous studies have identified the degradation of the solid electrolyte interphase (SEI) layer as the factor primarily responsible for the capacity loss seen at elevated temperatures. 1-4 Temperature-induced reactions, such as SEI decomposition, redox reaction, and electrolyte decomposition, cause changes in the morphology and composition of the SEI layer. 3 Deposition of transition metal ions, which are dissolved from the cathode active materials at elevated temperatures, onto the anode/electrolyte interface also contributes significantly to the degradation of the SEI layer. 5-7 Degradation of the SEI layer results in SEI reformation and growth, during which cyclable lithium ions are additionally consumed due to further electrolyte reduction reactions. Thus, the degraded SEI layer cannot sustain its original properties, which affects the degradation of anode performance. 1,3,7 For instance, an increase in the level of inorganic components present in the SEI layer can lower the ionic conductivity of the SEI layer, which hinders lithium ion transport into/from the anode. 4 While degradation of the SEI layer has been considered the main contributor to the fade in capacity at the anode side, several factors have been proposed as reasons for the capacity fade that comes from the cathode side. In particular, LiMn 2 O 4 shows the most severity in terms of (i) the dissolution of cathode materials due to the disproportionation reaction and hydrofluoric acid (HF) ...

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“…When the most active metal supplies current, it gradually dissolved into ions in the electrolyte. And at the same time produce electrons which the lease active will receive through the metallic connection with the anode [37]. The result obtained the variation of weight loss with exposure time, and the corresponding corrosion rate versus exposure time for coated and uncoated metals immersed in seawater for duration of 30 days or 4 weeks.…”

Section: Weight Loss Measurementmentioning

confidence: 95%

Corrosion behavior and resistance parameters of silicon carbide nanocomposite coating on different metals

Suriani¹,

Nik²,

Mansor³

et al. 2018

J. MECH. ENG. SCI.

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Silicon carbide (SiC) films were deposited on stainless steel (SS), mild steel (MS) and aluminium (Al) from a SiC targeted in a magnetron sputtering system to produce the amorphous SiC coating. Magnetron sputtering is a Physical Vapor Deposition process for deposited material onto substrate by ejecting atom from such SiC and condensing the ejected atom onto SS, MS and Al metals in high vacuum environment. The behavior of the films as corrosion protection barriers in different concentrations of sodium chloride (NaCl) solution in 0.5 M and 1.0 M at different temperatures (30 o C and 50 o C) were evaluated by electrochemical impedance spectroscopy (EIS) measurements. Films on SS exhibited a better corrosion resistance than MS and Al. The weight loss measurement, it shows that uncoated metals loss more weight than coated metals for longer time of immersion. Meanwhile the EIS results also depicted that the polarization resistance, (R p) coated metals indicates higher value compared to uncoated metals. The water salinity and temperatures also showed a significant effect on polarization resistance, (R p ) for both coated and uncoated metals. The R p are decreased with the increased of salinity and temperature accordingly. X-ray diffraction (XRD) used for determination of phase identification. Based on XRD, there are no higher peaks were obtained on SiC, and showed that SiC were confirmed amorphous. It concluded that this study shows corrosion rate of coated metals was decreased obviously compared to uncoated metals and SiC nanocomposite coating performed a significant corrosion behaviors and resistance parameter on different metals.

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Degradation of the solid electrolyte interphase induced by the deposition of manganese ions

Cited by 90 publications

References 44 publications

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

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

Effects of Fluoroethylene Carbonate (FEC) on Anode and Cathode Interfaces at Elevated Temperatures

Corrosion behavior and resistance parameters of silicon carbide nanocomposite coating on different metals

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