A review – exploring the performance degradation mechanisms of LiCoO<sub>2</sub> cathodes at high voltage conditions and some optimizing strategies

Wang, Chenyu; Weng, Jingzheng; Wu, Shuru; Zhang, Xian; Tong, Qingsong; Zhu, Mengqi

doi:10.1039/d2qm00342b

Cited by 11 publications

(4 citation statements)

References 180 publications

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“…6,26,29 The voltage curves in Figure 2b further demonstrate the rapid loss of capacity and imply that polarization growth plays a dominant role in the rapid capacity fade. The polarization could be caused by the ionically insulating spinel and rock-salt-type phases formed on the surface of the LCO particles at voltages >4.2 V. 7,30 The dQ dV −1 curves of the LP57 cells in Figure 2c shed additional light on the evolution of the polarization growth in LP57 cells. The initial oxidation peak, at roughly 3.8 V, shifts ∼200 mV higher after the formation cycles.…”

Section: ■ Results and Discussionmentioning

confidence: 97%

Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Adamo

Manthiram

2023

ACS Appl. Mater. Interfaces

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The commercialization of lithium-ion batteries started with a layered LiCoO 2 (LCO) cathode for portable electronics, but only 50% of its theoretical capacity can be used in practical cells due to detrimental surface and bulk degradations when charged to high voltages. We demonstrate here that the stability of the electrolyte plays a critical role in the performance of LCO at high voltages by employing a localized saturated electrolyte (LSE). With a cutoff voltage of 4.5 V, LCO achieves an initial 1 C discharge capacity of 176 mA h g −1 and a capacity retention of 80% over 230 cycles. Even with a cutoff voltage of 4.6 V, LCO with 2% aluminum doping displays an initial discharge capacity of 189 mA h g −1 at 1 C rate with 80% capacity retention over 137 cycles. With extensive analytical characterization, we show that the improved cycling stability stems from a suppression of the O3 to H1-3 phase transition as well as a robust inorganic-rich cathode−electrolyte interphase (CEI) facilitated by the LSE. This work highlights the importance of protecting the surface as well as the bulk with appropriate electrolytes for the high-voltage, higher-energy-density operation of LCO.

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Section: ■ Results and Discussionmentioning

confidence: 97%

Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Adamo

Manthiram

2023

ACS Appl. Mater. Interfaces

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“…Under high pressure, lithium cobalt oxide is often accompanied by irreversible and detrimental phase transitions starting from the surface. The internal stress changes caused hinder the lithium-ion transport in the materials, showing poor cycling performances and rate capabilities [17][18][19][20]. Furthermore, the higher delithiated LiCoO 2 (more than 0.5 Li removed at a cut-off voltage above 4.2 V) is highly oxidized, which could increase the likelihood of side reactions between the electrode materials and the electrolyte [21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Construction of Uniform LiF Coating Layers for Stable High-Voltage LiCoO2 Cathodes in Lithium-Ion Batteries

Xiao,

Zhu,

Wang

et al. 2024

Molecules

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Stabilizing LiCoO2 (LCO) at 4.5 V rather than the common 4.2 V is important for the high specific capacity. In this study, we developed a simple and efficient way to improve the stability of LiCoO2 at high voltages. After a simple sol–gel method, we introduced trifluoroacetic acid (TA) to the surface of LCO via an afterwards calcination. Meanwhile, the TA reacted with residual lithium on the surface of LCO, further leading to the formation of uniform LiF nanoshells. The LiF nanoshells could effectively restrict the interfacial side reaction, hinder the transition metal dissolution and thus achieve a stable cathode–electrolyte interface at high working-voltages. As a result, the LCO@LiF demonstrated a much superior cycling stability with a capacity retention ratio of 83.54% after 100 cycles compared with the bare ones (43.3% for capacity retention), as well as high rate performances. Notably, LiF coating layers endow LCO with excellent high-temperature performances and outstanding full-cell performances. This work provides a simple and effective way to prepare stable LCO materials working at a high voltage.

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“…Typically, the cycle stability of LCO electrode can be greatly deteriorated under an HT condition, which is usually regarded as the result of the intensified side reactions beyond 45 °C. [ 19 ] However, the mechanism of the intensified side reactions under HT condition still remains vague, which restricts the research and development of more advanced and practical LCO materials.…”

Section: Introductionmentioning

confidence: 99%

Multiple Surface Optimizations for a Highly Durable LiCoO₂ beyond 4.6 V

Li,

Yi,

Ren

et al. 2023

Adv Funct Materials

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Recently, lots of researches have focused on enhancing the structure stability of LiCoO2 (LCO) at a cutoff voltage of 4.6 V (vs Li/Li+) at room temperature. However, the high temperature (≥45 °C) performances are more significant for practical applications. Herein, the mechanism of unsatisfactory structure stability of LCO at 45 °C via comparing a commercial LCO (C‐LCO) and a surface optimized LCO (O‐LCO) is revealed first. The deteriorated structure stability of LCO at 45 °C is mainly due to two aspects: i) the promoted bulk Li+ ion diffusion kinetics at 45 °C leads to a higher state of charge for the charged LCO, which triggers more side reactions; ii) the more prominent surface structure collapse at 45 °C blocks the Li+ ion transport channels. Surface optimizations, including the anions (F− and PO43−) and cations (Al3+) surface modulation and a subsurface spinel reinforcement, are comprehensively applied to alleviate the side reaction and structure collapse issues of O‐LCO, leading to a high reversible discharge capacity of 238 mAh g−1, as well as an obviously enhanced cycle and floating stability at 45 °C and beyond 4.6 V. A new insight is provided here for developing more advanced and practical high‐voltage LCO.

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A review – exploring the performance degradation mechanisms of LiCoO₂ cathodes at high voltage conditions and some optimizing strategies

Abstract: High voltage enables batteries to have a larger capacity, which is indispensable for the development of new energy materials. However, the emergence of insecure problems and performance fading caused by...

Cited by 11 publications

References 180 publications

Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Construction of Uniform LiF Coating Layers for Stable High-Voltage LiCoO2 Cathodes in Lithium-Ion Batteries

Multiple Surface Optimizations for a Highly Durable LiCoO₂ beyond 4.6 V

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A review – exploring the performance degradation mechanisms of LiCoO2 cathodes at high voltage conditions and some optimizing strategies

Abstract: High voltage enables batteries to have a larger capacity, which is indispensable for the development of new energy materials. However, the emergence of insecure problems and performance fading caused by...

Cited by 11 publications

References 180 publications

Operation of Layered LiCoO2 to Higher Voltages with a Localized Saturated Electrolyte

Operation of Layered LiCoO2 to Higher Voltages with a Localized Saturated Electrolyte

Construction of Uniform LiF Coating Layers for Stable High-Voltage LiCoO2 Cathodes in Lithium-Ion Batteries

Multiple Surface Optimizations for a Highly Durable LiCoO2 beyond 4.6 V

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A review – exploring the performance degradation mechanisms of LiCoO₂ cathodes at high voltage conditions and some optimizing strategies

Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Operation of Layered LiCoO₂ to Higher Voltages with a Localized Saturated Electrolyte

Multiple Surface Optimizations for a Highly Durable LiCoO₂ beyond 4.6 V