Über Chalkogenolate. LXI. Untersuchungen über Halbester der Kohlensäure. 1. Darstellung und Eigenschaften von Monomethyl‐ und Monoäthylcarbonaten

Behrendt, Werner; Gattow, G.; Dräger, Martin

doi:10.1002/zaac.19733970303

Cited by 73 publications

(55 citation statements)

References 26 publications

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“…Comparing the calculated and experimental frequencies, 28 in which dramatic changes occurred between a monomer and a dimer, indicated good agreement with the experimental values.…”

Section: Resultssupporting

confidence: 76%

“…Calculated frequency values for dimers of EtOCO 2 Li and PrOCO 2 Li also indicated good agreement with the experimental values. 11,28 For example, in EtOCO 2 Li the vibrational frequency values of a CO 2 asymmetric stretching mode in the calculation for the dimer and in the experimental were 1654.2 and 1637 cm Ϫ1 , respectively. Values of its mode in PrOCO 2 Li were 1653.9 cm Ϫ1 (calculation) and 1650 cm Ϫ1 (experimental).…”

Section: Resultsmentioning

confidence: 99%

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Vibrational Assignments of Lithium Alkyl Carbonate and Lithium Alkoxide in the Infrared Spectra An Ab Initio MO Study

Matsuta

Asada

Kitaura

2000

J. Electrochem. Soc.

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Lithium electrode stability in various nonaqueous solvents is kinetic in origin and is caused by a film formed on the lithium surface by reaction of the active metal 1 or the active Li-C intercalation anode 2 with solvents. This film is called solid electrolyte interphase (SEI). 3-5 An SEI is formed at the negative electrode/electrolyte interface because of irreversible reactions. These reactions will ideally form a stable, protective film on negative electrode, allowing the electrode to continue to operate without further reaction. So the SEI passivation layer plays a major role in determining electrode and battery behavior and properties include cycle life, shelf life, safety, and irreversible capacity loss. Main components of an SEI are Li 2 CO 3 , ROCO 2 Li, ROLi, LiF, Li 2 O, and LiCl which are measured by techniques such as X-ray photoelectron spectroscopy, 6-10 infrared spectroscopy, 11-21 and X-ray diffractometry. 22,23 In addition, reaction gas products such as alkane, alkene, H 2 , CO 2 , and CO are measured by gas chromatography. 13,[24][25][26][27] Using an infrared spectroscopy, mainly observed components of an SEI are Li 2 CO 3 , ROCO 2 Li, and ROLi. Therefore standard data of these compounds are important of the investigation of the SEI with IR. For ROCO 2 Li-type compounds infrared spectra of the CH 3 OCO 2 Li, C 2 H 5 OCO 2 Li, C 3 H 7 OCO 2 Li, and C 4 H 7 OCO 2 Li have been measured by Behredt et al. 28 and infrared spectra of CH 3 CH(OCO 2 Li)CH 2 OCO 2 Li is obtained by Aurbach et al. 11 For ROLi-type compounds infrared spectra of the CH 3 OLi, C 2 H 5 OLi, C 4 H 9 OLi, LiOC 2 H 4 OLi, and LiOCH 2 CH(OLi)CH 3 have been measured by Aurbach et al. 11,12 There is not enough information for band assignments of the vibration modes of ROCO 2 Li-and ROLi-type compounds, so we calculated the structural information for these compounds. In this work, we calculated the geometry, energy, dipole moment, and norWe conducted ab initio molecular orbital calculations on stable monomer and dimer structures of lithium alkyl carbonates (methyl, ethyl, and propyl carbonate lithium) and lithium alkoxides (lithium methoxide, lithium ethoxide, lithium propoxide, and lithium butoxide). We confirmed that both lithium alkyl carbonates and lithium alkoxides adopted the dimer structure. The dimerization energies were approximately constant and independent of the alkyl group chain length. The dimerization energy was 214 kJ/mol for lithium alkyl carbonates and 266 kJ/mol for lithium alkoxides. Assignments of the vibration modes for each calculated frequency of lithium alkyl carbonates and lithium alkoxides were carried out. Vibrational frequency analysis recognized a dramatic vibrational frequency shift in the parts of the structure which changed significantly between the monomer and dimer structures (the lithium carbonate structure for lithium alkyl carbonates and the COLi structure for lithium alkoxides). Good agreement was achieved between calculated and experimental vibrational frequencies by shifting the frequency of ...

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“…Comparing the calculated and experimental frequencies, 28 in which dramatic changes occurred between a monomer and a dimer, indicated good agreement with the experimental values.…”

Section: Resultssupporting

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Vibrational Assignments of Lithium Alkyl Carbonate and Lithium Alkoxide in the Infrared Spectra An Ab Initio MO Study

Matsuta

Asada

Kitaura

2000

J. Electrochem. Soc.

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“…The calculated vibrational frequencies based on the dimer yields much better agreement with the experimental data than the monomer. Specifically [15], and repeated in the tabulation by Aurbach et al [7], the agreement with our experimental spectrum and band assignment is generally very close, with two notable differences. In the original tabulation, the strong bands near 1640 and 1100 cm -1 were reported to be doublets, whereas our spectrum clearly shows sharp single bands.…”

Section: Surface Films On Metallic Lithiumsupporting

confidence: 71%

Studies of Interfacial Chemistry in Lithium and Li-Ion Battery Systems Using Infrared Spectroscopy

Ross¹

2006

ECS Trans.

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Spectroscopic studies of the chemistry at electrochemical interfaces still face significant challenges even after decades of intense effort. No single methodology has emerged as the clear choice. Each method has advantages and disadvantages such that different types of interfacial chemistry are best studied by the methods that is the most advantageous for that chemistry. In this talk I present a review of recent studies in my laboratory of the chemistry at electrochemical interfaces using infrared reflection spectroscopy, with emphasis on use of attenuated total reflection spectroscopy (ATR) in the study of surface processes in Li-ion batteries.

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“…1b͒ shows a quadruplet at 3.49 ppm ͑ 3 J H-H = 6.9 Hz͒ and a triplet at 1.023 ppm ͑ 3 J H-H = 6.9 Hz͒, corresponding to the two and three hydrogens of -CH 2 and -CH 3 groups, respectively, while the 13 Fig. 2c, that we assigned to the presence of propanol within the sample, most likely resulting from the hydrolysis of lithium propyl carbonate 13 …”

Section: Resultsmentioning

confidence: 98%

Identification of Li Battery Electrolyte Degradation Products Through Direct Synthesis and Characterization of Alkyl Carbonate Salts

Gireaud

Grugeon

Laruelle

et al. 2005

J. Electrochem. Soc.

114

115

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Aiming toward the identification of carbonate-based electrolyte degradation species formed during high-temperature cycling of Li/M-O cells, we have embarked in the synthesis and characterization of lithium-based alkyl carbonates. Through the reaction of commercial or synthesized lithium alkoxides with carbon dioxide, we succeeded in preparing lithium methyl, ethyl, propyl mono carbonates, and therefore we have extended our work to the synthesis of lithium ethandiol-bis carbonate. Their analytical characterization ͑ 1 H and 13 C nuclear magnetic resonance, electrospray ionization-mass spectroscopy, Fourier transform: infrared/ attenuated total reflection͒ is described. Furthermore, to our surprise, we managed to demonstrate that these well-known alkyl carbonates show some electrochemical reactivity toward Li.Organic carbonates, because of their numerous attractive chemical properties, are used among others in pharmaceutical and energy storage applications as chemical synthesis precursors or as nonaqueous battery electrolyte, respectively. Mixtures of both cyclic carbonates ͓ethylene carbonate ͑EC͒ and/or propylene carbonate ͑PC͔͒ together with noncyclic ones ͓dimethyl carbonate ͑DMC͒ and/or ethyl methyl carbonate ͑EMC͔͒ are among the most employed solvent combinations in the preparation of today's electrolytes for Li-based batteries. Their attractiveness is nested in their high electrochemical stability toward lithium combined with a high dielectric constant provided by cyclic carbonates, which favors ion separation, and a decent viscosity provided by the suitable addition of noncyclic carbonates. Due to their key role in the proper functioning of Li-based cells, many studies have already been carried out on Li-based carbonate electrolytes, and numerous reports describing their properties and their Li-driven reduction mechanisms leading to the growth of the well-known solid electrolyte interphase ͑SEI͒ at the Li surface are available. 1-6 Usually, besides Li 2 CO 3 , alkyl carbonates are reported as the most common species resulting from electrolyte reduction with occasionally the possibility of forming poly͑ethylene oxide͒ ͑PEO͒ oligomers. However, some uncertainties still remain not only on the exact nature of the alkyl-carbonate formed, which can be mono or bis-carbonates, but also on the exact composition of this SEI layer. Attempts to answer such questions are quite a tedious task due to ͑i͒ the usually limited growth ͑e.g., small amount of materials͒ of the SEI so that we must rely on passive analytical techniques ͓Fourier transform infrared ͑FTIR͒, AC-impedance spectroscopy͔, and ͑ii͒ the highly air/moisture sensitivity of the Li-based materials so that results of surface characterization analyses, such as atomic force microscopy ͑AFM͒ or X-ray photoelectron spectroscopy ͑XPS͒, could largely differ among research groups. 7 Recently, in studying the electrochemical reactivity of 3d-metal oxides ͑CoO, Co 3 O 4 , CuO. . .͒ toward Li, we unraveled a novel reactivity mechanism. Such materials were shown to rever...

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Über Chalkogenolate. LXI. Untersuchungen über Halbester der Kohlensäure. 1. Darstellung und Eigenschaften von Monomethyl‐ und Monoäthylcarbonaten

Cited by 73 publications

References 26 publications

Vibrational Assignments of Lithium Alkyl Carbonate and Lithium Alkoxide in the Infrared Spectra An Ab Initio MO Study

Vibrational Assignments of Lithium Alkyl Carbonate and Lithium Alkoxide in the Infrared Spectra An Ab Initio MO Study

Studies of Interfacial Chemistry in Lithium and Li-Ion Battery Systems Using Infrared Spectroscopy

Identification of Li Battery Electrolyte Degradation Products Through Direct Synthesis and Characterization of Alkyl Carbonate Salts

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