Kinetic Study of Boric Acid-Borate Interchange in Aqueous Solution by 11B NMR Spectroscopy

Ishihara, Koji; Nagasawa, Akira; Umemoto, Kimiko; Ito, Hideaki; Saitō, Kazuo

doi:10.1021/ic00095a026

Cited by 56 publications

(47 citation statements)

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“…The integrated ratio of methyl protons to aromatic protons is 4:6, which matches the structure of LiCDMB. A single peak characteristic of the product at 7.7 ppm is observed in the 11 B NMR spectrum, 11 B chemical shift of boric acid located between −20-0ppm as a function of pH, 51 suggesting LiCDMB doesn't decompose into boric acid in D 2 O. The 1 H and 11 B NMR spectra support the isolation of a pure compound.…”

Section: Resultsmentioning

confidence: 67%

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi_0.5Mn_1.5O₄Cells with Added Lithium Catechol Dimethyl Borate

Dong

Demeaux

Zhang

et al. 2016

J. Electrochem. Soc.

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Performance of LiNi 0.5 Mn 1.5 O 4 /graphite cells cycled to 4.8 V at 55 • C with the 1.2 M LiPF 6 in EC/EMC (3/7, STD electrolyte) with and without added lithium catechol dimethyl borate (LiCDMB) has been investigated. The incorporation of 0.5 wt% LiCDMB to the STD electrolyte results in an improved capacity retention and coulombic efficiency upon cycling at 55 • C. Ex-situ analysis of the electrode surfaces via a combination of SEM, TEM, and XPS reveals that oxidation of LiCDMB at high potential results in the deposition of a passivation layer on the electrode surface, preventing transition metal ion dissolution from the cathode and subsequent deposition on the anode. NMR investigations of the bulk electrolyte stored at 85 Lithium-ion batteries are widely used for portable electronics and are currently being incorporated into electric vehicles due to their high energy density.1,2 However, there is significant interest in further increasing the energy density of lithium-ion batteries.3 One method to achieve higher energy density is increasing the operating potential of the cathode material. Most commercial lithium-ion batteries contain a lithiated transition metal oxide cathode that typically operates at ∼4.0 V vs. Li/Li + . 3,4 Several novel cathode materials with operating potentials over 4.0 V are currently under investigation, including LiNiPO 4 , 5 LiCoPO 4 , 5,6 and LiNi 0.5 Mn 1.5 O 4 . While the high operating potential of the LiNi 0.5 Mn 1.5 O 4 spinel cathode (4.8 V vs. Li/Li + ) offers high energy density, commercialization has been hampered by severe capacity fade and poor efficiency. 7 The capacity fade is particularly pronounced at moderately elevated temperatures (>45• C) and in full cells employing a graphite anode. 7 The failure mechanisms of LiNi 0.5 Mn 1.5 O 4 cells at high voltage and elevated temperature have been recently investigated. [8][9][10][11][12][13][14] Electrolyte decomposition, electrode/electrolyte interface degradation, and transition metal dissolution are the leading factors reported for performance fade. One effective method for improving the performance of high voltage cathodes involves the incorporation of SEI (solid electrolyte interface) and CEI (cathode electrolyte interface) forming electrolyte additives that are sacrificially oxidized on the surface of electrodes to generate a passivation film which inhibits transition metal dissolution and further electrolyte oxidation.There have been several reports where electrolyte additives have improved the performance of cathodes cycled to high potential. [15][16][17][18]23 Lithium bis(oxalato borate) (LiBOB) has been reported to be one of the better additives for LiNi 0.5 Mn 1.5 O 4 cathodes. 16,17,[20][21][22][23][24][25] The related additive, lithium difluorooxalato borate (LiDFOB) 27-31 has also been reported to improve the properties of Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 cathodes cycled to high potential 19 In addition to the lithium oxalato borates, 26,32 we have recently reported on the beneficial effect of the incorpor...

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Section: Resultsmentioning

confidence: 67%

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi_0.5Mn_1.5O₄Cells with Added Lithium Catechol Dimethyl Borate

Dong

Demeaux

Zhang

et al. 2016

J. Electrochem. Soc.

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“…The technique used was based on the principle of the diffusion method described by Blyth et al [26] For these 2-APB acrylamide-based copolymers the procedure described previously [15,24] was used. All of this work was carried out under safe red lighting.…”

Section: Methodsmentioning

confidence: 99%

Complexation of L‐Lactate with Boronic Acids: A Solution and Holographic Analysis

Sartain

Yang

Lowe

2008

Chemistry A European J

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Boronic acids have been used as receptors for the detection of diols and alpha-hydroxy acids. The incorporation of 3-acrylamide phenyl boronic acid (3-APB) into a hydrogel generates a suitably responsive and fully reversible holographic sensor for L-lactate. However, it was also found that the use of 3-APB resulted in the sensor being responsive towards a number of other compounds containing two hydroxy groups. This report details the further investigation into the reaction between L-lactate and three boronic acid-based receptors, both in the holograms and in solution, in order to establish the mechanism of binding. A novel boronate receptor is proposed based on this understanding.

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“…The Lewis acidity of the free boronic acid is lower than that of the trigonal ester; for example, Wang et al [4] reported that the pK a values of phenylboronic acid decreased from 8.8 to 6.8 and 4.5 upon formation of cyclic esters with glucose and fructose, respectively, although it was suggested by Bosch et al that these pK a values were erroneous. [2] Unfortunately, these schemes cannot explicitly explain the following findings, which are observed for the complexation of boronic acids with bidentate ligands: [5][6][7][8][9][10][11] (1) the boronate ion [RB(OH) 3 À ] reacts with diols (H 2 L) only in neutral to alkaline sol-alkaline solutions, but reacts easily with bidentate ligands with low pK a values, such as chromotropic acid (a reagent for the detection of boron, pK a = 5.35), Tiron (a reagent for the detection of Ti and Fe, pK a = 6.87), and alizarin red S (pK a = 5.33) in acidic aqueous solutions as well as in alkaline solutions; (3) the amount of complex formed increases with increasing pH value to a maximum, and then decreases. The establishment of an appropriate reaction mechanism is therefore essential.…”

Section: Introductionmentioning

confidence: 99%

Universal Reaction Mechanism of Boronic Acids with Diols in Aqueous Solution: Kinetics and the Basic Concept of a Conditional Formation Constant

Furikado

Nagahata

Okamoto

et al. 2014

Chemistry A European J

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104

115

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To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red S, and phenylboronic acid and alizarin red S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a) the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b) the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)⇌ RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH 5-11: B' + L' (K')⇌ BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution.

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Kinetic Study of Boric Acid-Borate Interchange in Aqueous Solution by 11B NMR Spectroscopy

Cited by 56 publications

References 0 publications

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi_0.5Mn_1.5O₄Cells with Added Lithium Catechol Dimethyl Borate

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi_0.5Mn_1.5O₄Cells with Added Lithium Catechol Dimethyl Borate

Complexation of L‐Lactate with Boronic Acids: A Solution and Holographic Analysis

Universal Reaction Mechanism of Boronic Acids with Diols in Aqueous Solution: Kinetics and the Basic Concept of a Conditional Formation Constant

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Kinetic Study of Boric Acid-Borate Interchange in Aqueous Solution by 11B NMR Spectroscopy

Cited by 56 publications

References 0 publications

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi0.5Mn1.5O4Cells with Added Lithium Catechol Dimethyl Borate

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi0.5Mn1.5O4Cells with Added Lithium Catechol Dimethyl Borate

Complexation of L‐Lactate with Boronic Acids: A Solution and Holographic Analysis

Universal Reaction Mechanism of Boronic Acids with Diols in Aqueous Solution: Kinetics and the Basic Concept of a Conditional Formation Constant

Contact Info

Product

Resources

About

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi_0.5Mn_1.5O₄Cells with Added Lithium Catechol Dimethyl Borate

Improving the Performance at Elevated Temperature of High Voltage Graphite/LiNi_0.5Mn_1.5O₄Cells with Added Lithium Catechol Dimethyl Borate