Anodic oxidation of propylene carbonate and ethylene carbonate on graphite electrodes

Arakawa, Masayasu; Yamaki, Jun‐ichi

doi:10.1016/0378-7753(94)02078-h

Cited by 93 publications

(72 citation statements)

References 7 publications

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“…This indicates that recharging the cell involves not only a reduction of lithium peroxide but also electrolyte decomposition (propylene carbonate was used as electrolyte in most of the works, where the charge properties of Li-air electrode were studied) [45,46], letting alone apparently low Fig. 4.…”

Section: Air Cathode Catalyst and Li-air Cell Performancementioning

confidence: 99%

Review on Li–air batteries—Opportunities, limitations and perspective

Kraytsberg

Ein‐Eli

2011

Journal of Power Sources

555

406

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Section: Air Cathode Catalyst and Li-air Cell Performancementioning

confidence: 99%

Review on Li–air batteries—Opportunities, limitations and perspective

Kraytsberg

Ein‐Eli

2011

Journal of Power Sources

555

406

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“…[8][9][10][11][12][13][14] Recently, a detailed mechanism on the oxidative decomposition of PC was given with theoretical calculations. 15 Similarly, a wide variety of experimental techniques have been used 5,16 to determine the reduction mechanism of EC.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory calculations for the interaction of Li⁺ cations and PF₆^– anions with nonaqueous electrolytes

2011

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The interaction of lithium (Li + ) cation and hexafluorophosphate (PF6 -) anion with nonaqueous electrolytes is studied by using density functional theory at the B3LYP/6-311++G(d,p) level in the gas phase in terms of the coordination of Li + and PF6 -with these solvents. Ethylene carbonate (EC) coordinates with Li + and PF6 -most strongly and reaches the anode and cathode most easily because of its highest dielectric constant among all the solvent molecules, resulting in its preferential reduction on the anode and oxidation on the cathode. For cyclic carbonates EC and propylene carbonate (PC), the structure Li + (S)4 is found to be the most stable. However, for linear carbonates dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC), the formation of PF6 -(S)n=1-3 is not favorable. Such analysis may be useful in applications for lithium ion batteries.Résumé : Faisant appel à la théorie de la fonctionnelle de la densité au niveau B3LYP/6-311++G(d,p), on a étudié d'un point de vue théorique l'interaction du cation lithium (Li + ) et de l'anion hexafluorophosphate (PF6 -) avec des électrolytes non aqueux, en phase gazeuse, en termes de la coordination du (Li + ) et du (PF6 -) avec ces solvants. Le carbonate d'éthylène (CE) est celui qui donne la coordination la plus forte avec le (Li + ) et le (PF6 -) et il atteint l'anode et la cathode le plus facilement en raison de sa constante diélectrique qui est la plus élevée de toutes les molécules de solvant; il en résulte que sa réduction à l'anode et son oxydation à la cathode sont les réactions privilégiées. Pour les carbonates cycliques, tel le CE et le carbonate de phénylène (CP), on a trouvé que la structure Li + (S)4 est la plus stable. Toutefois, pour les carbonates linéaires, tel le carbonate de diméthyle (CDM), le carbonate de diéthyle (CDE) et le carbonate d'éthyle et de méthyle (CEM), la formation de la structure Li + (S) n=1-3 n'est pas favorisée. Une telle analyse peut être utile dans les applications de batteries au lithium.Mots-clés : théorie de la fonctionnelle de la densité, solvants, stabilité, exothermique, oxydation, chaleur de formation.[Traduit par la Rédaction]

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“…5c͒, it is most reasonable to propose EC as the source, and in analogy to the suggestion by Arakawa and Yamaki, 25 follows the following mechanism involving a 1,2-proton shift Because of the effect of electric fields, CH 3 COO Ϫ is concentrated on the positive electrode surface, and the electron cloud on the carboxyl (-COO Ϫ ) is attracted by the positive charge electrode surface. Therefore the ␤-C of CH 3 COO Ϫ is electropositive due to the induction effect and it is easily attacked by CH 3 • , which comes from the decomposition of DMC.…”

Section: Resultsmentioning

confidence: 97%

Comparison of Electrochemical and Surface Properties of Bare and TiO[sub 2]-Coated LiNi[sub 0.8]Co[sub 0.2]O[sub 2] Electrodes

Zhang

Liu

Gong

et al. 2004

J. Electrochem. Soc.

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The electrochemical behaviors of native and TiO 2 -coated LiNi 0.8 Co 0.2 O 2 electrodes which were cycled in different potential regions ͑i.e., 3.0-4.3 and 3.0-4.6 V͒ were investigated by the powder microelectrode technique. The surface species on the electrodes were also studied by Fourier transform infrared and temperature-programmed desorption-mass spectroscopy ͑TPD-MS͒ techniques. Different oxidation products were formed on the bare and coated electrodes, respectively. The results indicated that the improved cyclic stability of the coated electrodes may be attributed to formation of different surface oxide films through an electro-oxidation mechanism of the solvents on the electrodes. A possible electro-oxidation mechanism has been proposed based on the results. LiNi 0.8 Co 0.2 O 2 is a candidate for a cathode material with high capacity and reasonable thermal properties for lithium-ion batteries. 1 However, LiNi 0.8 Co 0.2 O 2 fades capacity relatively rapidly when the upper cutoff potential is set above 4.3 V. 2-4 Recently, sol-gel coating of various metal oxides has been reported to improve cyclic performance, for example, LiNiO 2 with ZrO 2 5 coating, LiNi 0.8 Co 0.2 O 2 with TiO 2 coating, 6 and other cathode materials with various metal oxide coatings. 7-14 All these coated materials exhibited good cycle stability when cycled to a higher potential of ϳ4.5 V. However, the mechanism of improved cycling behavior generated by coating is still not clear. Some authors suggested that a thin coating layer suppressed the lattice expansion of cathode materials during cycling that resulted in improved behavior, 9,10 whereas other authors thought the coating may inhibit side reactions involving oxygen transfer from the material to the electrolyte 7 or the oxidation of the electrolyte. 4 Therefore, it is helpful to understand the decomposition mechanism of the electrolyte through the study of the decomposition products on the electrode surface.Powder microelectrode technique is a direct way to evaluate the electrochemical characteristics of the active materials without the interference of binder and conductive additives. 15,16 Because the measured current is very small ͑nanoampere level͒, the internal resistance (iR) potential drop of the working electrodes may be neglected. The voltammetric behavior of powder materials is affected mainly by the diffusion rate of Li ions inside the particles.Spectroscopic techniques may provide direct evidence to study and understand the electrode reaction mechanism at a molecular/ atomic level. For example, Fourier transform infrared ͑FTIR͒ is a powerful technique for characterizing the absorbed species on the material surface, and temperature-programmed desorption-mass spectroscopy ͑TPD-MS͒ may be applied to obtain the mass-electric charge ratio (m/e) of the species adsorbed on the material surface. The combination of the two techniques should help us to determine species adsorbed on the electrode surface confidently. To the best of our knowledge, in the field of rechargeable lit...

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Anodic oxidation of propylene carbonate and ethylene carbonate on graphite electrodes

Cited by 93 publications

References 7 publications

Review on Li–air batteries—Opportunities, limitations and perspective

Review on Li–air batteries—Opportunities, limitations and perspective

Density functional theory calculations for the interaction of Li⁺ cations and PF₆^– anions with nonaqueous electrolytes

Comparison of Electrochemical and Surface Properties of Bare and TiO[sub 2]-Coated LiNi[sub 0.8]Co[sub 0.2]O[sub 2] Electrodes

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Anodic oxidation of propylene carbonate and ethylene carbonate on graphite electrodes

Cited by 93 publications

References 7 publications

Review on Li–air batteries—Opportunities, limitations and perspective

Review on Li–air batteries—Opportunities, limitations and perspective

Density functional theory calculations for the interaction of Li+ cations and PF6– anions with nonaqueous electrolytes

Comparison of Electrochemical and Surface Properties of Bare and TiO[sub 2]-Coated LiNi[sub 0.8]Co[sub 0.2]O[sub 2] Electrodes

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Density functional theory calculations for the interaction of Li⁺ cations and PF₆^– anions with nonaqueous electrolytes