Mechanism of gas evolution from the cathode of lithium-ion batteries at the initial stage of high-temperature storage

Kim, Yongseon

doi:10.1007/s10853-013-7673-2

Cited by 66 publications

(53 citation statements)

References 13 publications

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Section: Residual Lithium Compoundsmentioning

confidence: 99%

“…[32,33] Furthermore, at the fully charged state, the residual lithium compounds also gave rise to the carbon dioxide gas evolution by reacting with the electrolyte solvent and acidic species formed by decomposition of the polymeric binder. [13,30,34] It was reported that the amount of residual lithium compounds was responsible for the gas evolution during the storage test at the fully charged state and high temperature of 85 °C. [13] As shown in Figure 1e, the initial amount of gas evolution in the pristine LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM) and the NCM mixed with 5 wt% of Li 2 CO 3 showed significant difference.…”

Section: −•mentioning

confidence: 99%

“…[13,30,34] It was reported that the amount of residual lithium compounds was responsible for the gas evolution during the storage test at the fully charged state and high temperature of 85 °C. [13] As shown in Figure 1e, the initial amount of gas evolution in the pristine LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM) and the NCM mixed with 5 wt% of Li 2 CO 3 showed significant difference. The pristine NCM evolved the gas of ≈1 cc g −1 ; for comparison, the NCM + Li 2 CO 3 5 wt% revealed ≈7 cc g −1 after the storage for 10 d. However, the rate of volume expansion of the cell (ΔV Δt −1 ) was identical for both samples as time passed.…”

Section: −•mentioning

confidence: 99%

“…[8][9][10][11] The Li 2 CO 3 significantly promotes the gas evolution and increase the moisture of the cathode powder, which strongly related to the safety issue. [12][13][14] Furthermore, the LiOH on the cathode increases the powder pH value, causing the gelation of the slurry during the electrode fabrication process. The nickel-rich cathode with nickel content of ≤60% have acceptable amount of residual lithium compounds for the practical use.…”

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confidence: 99%

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Prospect and Reality of Ni‐Rich Cathode for Commercialization

Kim

Lee

Cha

et al. 2017

Advanced Energy Materials

639

582

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practical candidate for the wide application of the LIBs with respect to the reversible capacity, rate capability, and capital cost. [4][5][6][7] In terms of nickel contents, the nickel-rich cathodes with nickel content above 80% have advantages in gravimetric capacity, allowing high gravimetric energy density, compared with the nickel content less than 80%. Currently, the nickel-rich cathodes with the amount of nickel less than 60% are fully commercialized. However, the nickel-rich cathodes with nickel content of ≥80% still have many difficulties in the commercialization with respect to powder properties and electrode fabrication process.The unstable powder properties originate from residual lithium compounds such as LiOH and Li 2 CO 3 that formed by the spontaneous reduction of sensitive trivalent nickel ions during the synthesis process and storage in air. [8][9][10][11] The Li 2 CO 3 significantly promotes the gas evolution and increase the moisture of the cathode powder, which strongly related to the safety issue. [12][13][14] Furthermore, the LiOH on the cathode increases the powder pH value, causing the gelation of the slurry during the electrode fabrication process. The nickel-rich cathode with nickel content of ≤60% have acceptable amount of residual lithium compounds for the practical use. By contrast, the cathode with amount of nickel of ≥80% should be treated by additional process to reduce the residual lithium compounds ( Table 1). Furthermore, other powder properties, such as powder pH and moisture, should be carefully controlled when nickel contents were exceeded of ≥80%. Thus, for the practical application of these cathode materials, most battery companies have adapted the washing process, in which the cathode power was stirred in purified water for 20-40 min. [15,16] The washing process could greatly reduce the residual lithium compounds and powder pH value. [15] However, the washing process not only increases process time and capital cost but also make the nickel-rich cathode more chemically sensitive than nonwashed cathodes. [16] More seriously, the water washing deteriorates the thermal stability of the nickel-rich cathodes, indicating that the washing process should be substituted by other methods for the battery safety.Another important factor for the commercialization of the nickel-rich cathodes is the electrode density directly related to the energy density. In general, the nickel-rich cathodesThe layered nickel-rich cathode materials are considered as promising cathode materials for lithium-ion batteries (LIBs) due to their high reversible capacity and low cost. However, several significant challenges, such as the unstable powder properties and limited electrode density, hindered the practical application of the nickel-rich cathode materials with the nickel content over 80%. Herein, important stability issues and in-depth understanding of the nickel-rich cathode materials on the basis of the industrial electrode fabrication condition for the commercialization of the nickel-rich cathode m...

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Section: Residual Lithium Compoundsmentioning

confidence: 99%

Section: −•mentioning

confidence: 99%

Section: −•mentioning

confidence: 99%

mentioning

confidence: 99%

See 2 more Smart Citations

Prospect and Reality of Ni‐Rich Cathode for Commercialization

Kim

Lee

Cha

et al. 2017

Advanced Energy Materials

639

582

View full text Add to dashboard Cite

show abstract

“…It was found that the Ni-based layer-structure positive electrode material contained more residues of lithium compounds, such as Li 2 CO 3 or LiOH, and their side reaction with electrolyte solution has been proposed to be the main cause of gas evolution at the initial stages of the storage test. Regarding LCO, it was proposed that the relatively slow but steady reaction between the material itself (i.e., LiCoO 2 ) and the electrolyte solution is the main mechanism for gas evolution [7,10]. Nevertheless, more research is required to provide a better explanation and an effective prevention measure for gas evolution.…”

Section: Introductionmentioning

confidence: 99%

First-principles investigation of the gas evolution from the cathodes of lithium-ion batteries during the storage test

2014

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Gas evolution related to the positive electrode of charged lithium-ion batteries during the storage test was investigated using a first-principle method. The distribution of lithium during the delithiation process was simulated based on the density functional theory calculations of the energy required to remove the lithium from the surface or bulk crystal of lithium nickel cobalt manganese oxide (NCM) and lithium cobalt oxide (LCO). Lithium coverage of the surface was smaller for LCO than NCM at a highly charged state. The energy required to form an oxygen vacancy in NCM and LCO crystal was also calculated. The results showed that LCO was more apt to emit oxygen than NCM as the delithiation percentage was increased. The results suggest that the gas-generating side reactions related to the emission of oxygen would be more significant for LCO with high voltage charging. Experimental result showed a considerable portion of the gas was generated at the initial stages of storage for NCM, whereas LCO showed slow but steady gas evolution with increasing storage time. A large amount of Li 2 CO 3 or LiOH on the surface of NCM appears to cause an immediate gas-generating side reaction, whereas LCO produces slow side reaction related to the emission of oxygen from the LCO material itself.

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Controllable Solid Electrolyte Interphase in Nickel‐Rich Cathodes by an Electrochemical Rearrangement for Stable Lithium‐Ion Batteries

Kim

Lee

et al. 2017

Advanced Materials

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The layered nickel-rich materials have attracted extensive attention as a promising cathode candidate for high-energy density lithium-ion batteries (LIBs). However, they have been suffering from inherent structural and electrochemical degradation including severe capacity loss at high electrode loading density (>3.0 g cm ) and high temperature cycling (>60 °C). In this study, an effective and viable way of creating an artificial solid-electrolyte interphase (SEI) layer on the cathode surface by a simple, one-step approach is reported. It is found that the initial artificial SEI compounds on the cathode surface can electrochemically grow along grain boundaries by reacting with the by-products during battery cycling. The developed nickel-rich cathode demonstrates exceptional capacity retention and structural integrity under industrial electrode fabricating conditions with the electrode loading level of ≈12 mg cm and density of ≈3.3 g cm . This finding could be a breakthrough for the LIB technology, providing a rational approach for the development of advanced cathode materials.

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Mechanism of gas evolution from the cathode of lithium-ion batteries at the initial stage of high-temperature storage

Cited by 66 publications

References 13 publications

Prospect and Reality of Ni‐Rich Cathode for Commercialization

Prospect and Reality of Ni‐Rich Cathode for Commercialization

First-principles investigation of the gas evolution from the cathodes of lithium-ion batteries during the storage test

Controllable Solid Electrolyte Interphase in Nickel‐Rich Cathodes by an Electrochemical Rearrangement for Stable Lithium‐Ion Batteries

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