Electrochemical Surface Analysis of LiMn&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt; Thin-film Electrodes in LiPF&lt;sub&gt;6&lt;/sub&gt;/Propylene Carbonate at Room and Elevated Temperatures

Inamoto, Junichi; Fukutsuka, Tomokazu; Miyazaki, Kohei; Abe, Takeshi

doi:10.5796/electrochemistry.20-00112

Cited by 5 publications

(4 citation statements)

References 36 publications

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“…This suggests that the reactions of acidic species generated from electrolyte oxidation on the cathode are more likely to cross over and damage the anode SEI than the dissolved transition metals. Since F 2 PO 2 H is also one of the species involved in the thermal autocatalytic decomposition of LiPF 6 in carbonates, this provides a good explanation for the significant difference in capacity retention upon a relatively small change in temperature (25 °C vs 45 °C). , Thus, developing electrolyte formulations or metal oxide surface films which inhibit the oxidation of LiPF 6 and EC to generate F 2 PO 2 H would lead to improve capacity retention in high voltage lithium ion batteries.…”

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confidence: 99%

“…17,26 Thus, developing electrolyte formulations or metal oxide surface films which inhibit the oxidation of LiPF 6 and EC to generate F 2 PO 2 H would lead to improve capacity retention in high voltage lithium ion batteries. sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsenergylett.1c01657.…”

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confidence: 99%

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Role of Electrolyte Oxidation and Difluorophosphoric Acid Generation in Crossover and Capacity Fade in Lithium Ion Batteries

et al. 2021

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Poor cycling performance for many high voltage lithium ion batteries (LIB) has been attributed to damage of the anode solid electrolyte interphase (SEI) resulting from crossover reactions. Transition-metal ion crossover has been proposed as a primary source of SEI damage and capacity loss, especially for high-voltage spinel cathodes. However, deposition of transition metals on the anode SEI may not be the primary source of SEI degradation. This investigation focuses on the oxidative decomposition of LiPF 6 in ethylene carbonate (EC)-based carbonate electrolytes to generate acidic species which subsequently cross over to the anode and degrade the anode SEI components. The generation of the strong acid, difluorophosphoric acid (F 2 PO 2 H), has been quantified for both graphite || LiNi 0.5 Mn 1.5 O 4 and graphite || LiMn 2 O 4 cells. There is a correlation between the concentration F 2 PO 2 H, SEI degradation, and the capacity loss of the cells.

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confidence: 99%

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Role of Electrolyte Oxidation and Difluorophosphoric Acid Generation in Crossover and Capacity Fade in Lithium Ion Batteries

et al. 2021

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“…It is well known that the serious capacity degradation of lithium batteries at high temperatures is a long-standing issue. High temperatures accelerate the occurrence of parasitic side reactions. − Interestingly, the Li/CPE/LiFePO 4 battery at 55 °C presented improved capacity retention without detectable degradation over 100 cycles (Figure f) due to the high-temperature electrochemical stability of the obtained P(EGDMA-EDT)-based electrolyte.…”

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confidence: 99%

Facile and Powerful In Situ Polymerization Strategy for Sulfur-Based All-Solid Polymer Electrolytes in Lithium Batteries

Xiao

Xuan

et al. 2021

ACS Appl. Mater. Interfaces

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All-solid-state polymer electrolytes can improve the safety of lithium batteries. However, the common Bellcore polymer electrolyte technology faces several issues such as wasting a mass of solvent, high manufacturing cost, and poor interfacial compatibility between polymer electrolytes and electrodes. Herein, we propose an in situ polymerization technique to synthesize all-solid-state polymer electrolytes by a thiol-Michael addition click reaction. The alternating copolymer is made from the Michael addition reaction of ethylene glycol dimethacrylate (EGDMA) and 1,2-ethane dithiol (EDT). At ambient temperature, the obtained composite polymer electrolyte displays an ionic conductivity of 3.02 × 10–5 S/cm, an electrochemical window of 4.5 V, and a lithium-ion transference number of 0.45. In light of this unique polymerization process, the traditional fabrication method of liquid electrolyte-based lithium batteries can be adopted in the current study for the preparation of all-solid-state Li/LiFePO4 batteries. It was found that the assembled all-solid-state Li/LiFePO4 batteries exhibited superior charging/discharging performance and preferable safety. Thus, this facile and powerful in situ polymerization strategy may open up a new approach for the design and fabrication of all-solid-state batteries with desirable performances.

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“…Thus far, we have investigated surface film formation behavior on various cathode materials. [15][16][17][18][19][20] As a result, we have found that the surface film was not always formed on cathode materials, and the formation behavior largely depended on the situation. For example, we have reported that the surface film formation behavior is greatly affected by the stability of lithium salt, temperature, and dissolution behaviors of transition metals.…”

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confidence: 93%

Effect of the Oxygen Evolution from Lithium-Rich Cathode Materials on the Formation Behavior of Passivation Surface Film

Inamoto

Baskoro

Matsuo

2023

J. Electrochem. Soc.

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It has been reported that lithium-rich cathode materials of LIB emit singlet oxygen during charging, which chemically oxidizes electrolyte solutions, and the decomposition products form surface film on the material. However, the detailed conditions and mechanism of the surface film formation and its effect on the electrochemical reaction at the electrode/electrolyte interface have not been clarified in detail. In this study, using 0.5LiCoO2 • 0.5Li2MnO3 thin-film electrodes as the model electrodes of the lithium-rich cathode materials, the surface film formation behavior was investigated. After a constant current-constant voltage (CCCV) measurement to 4.8 V, passivation of the electrodes did not occur. On the other hand, the electrode after cyclic voltammetry (CV) up to 4.8 V showed complete passivation. The results of spectroscopic analyses revealed that decomposition products of the solvent formed thick surface film on the electrode after CV. From the results, it was concluded that the passivation surface film was formed by the simultaneous decomposition of the solvent via electrochemical oxidation at high potentials and chemical oxidation by singlet oxygen. Furthermore, the electrode with the surface film showed better cycleability than that without the surface film, indicating that it contributes to the suppression of side reactions at the electrode/electrolyte interface.

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Electrochemical Surface Analysis of LiMn<sub>2</sub>O<sub>4</sub> Thin-film Electrodes in LiPF<sub>6</sub>/Propylene Carbonate at Room and Elevated Temperatures

Cited by 5 publications

References 36 publications

Role of Electrolyte Oxidation and Difluorophosphoric Acid Generation in Crossover and Capacity Fade in Lithium Ion Batteries

Role of Electrolyte Oxidation and Difluorophosphoric Acid Generation in Crossover and Capacity Fade in Lithium Ion Batteries

Facile and Powerful In Situ Polymerization Strategy for Sulfur-Based All-Solid Polymer Electrolytes in Lithium Batteries

Effect of the Oxygen Evolution from Lithium-Rich Cathode Materials on the Formation Behavior of Passivation Surface Film

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