Borate Additives

Lithium bis(oxalato) borate was investigated as an additive for the stabilization of a high-voltage cathode electrolyte interface (57). It has been found that the electrochemical performance of Li/LiNio.5Mni.504 cells with a hthium bis(oxalato) borate additive was improved at 60°C. 

The effects of lithium bis(oxalato) borate on the electrolyte oxidative decomposition, the surface chemistry of separators and the cathodes cycled in electrolytes with and without a lithium bis(oxala-to) borate additive were assessed using ATR-FTIR spectroscopy and XPS (57). 

As cathode LiFeP04 was used and as electrolyte, 1 M LiPFe in a 1 1 mixture of ethylene carbonate and ethylene carbonate at 25 C and 60 C was used. 

Triphenyl borate shows the formation of a thick surface/electro-lyte interface which inhibits the ion flow and does not protect the electrode from degradation. Although useful at 25°C, triphenyl borate at 60°C results in only 7% capacity after 100 cycles. 

On the other hand, 0.1 M trimethyl borate results in 53% capacity. The trimethyl borate performance improves with increasing concentration. Trimethyl borate also suppresses the thermal decomposition of the electrolyte and the formation of the surface/electrolyte interface film (58). 

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Catacarb Aqueous Potassium Carbonate with Borate Additive Blocks pores of catalyst by evaporation of K2CO3 solution. 

Only transition metal catalyzed stereoselective versions of these reactions, leading to isolable (or at least potentially isolable) organometallic carbometalation products, are described in this section. For methods which use carbometalation as a single step in catalytic cycles, with Further conversion of the reactive intermediates to form hydrocarborated, dicarborated or heterocar-borated addition products, see other parts of Section 1.5.8.4. 

In these experiments, unaltered Sweetzyme at pH 7.5 was used. In the absence of borate, addition of metal ions results in a small shift in the isomerization toward xylulose (Fig. 8, curves A and B). In the presence of borate, a similar shift in the isomerization is... 

Buffer 5 mM chromate or phthalate, pH 10.00 5 mM chromate, pH 8.0 5 mM chromate, pH 11.0 (LiOH) 30 mM creatinine, pH 4.8 (acetic acid) 100 mM borate Additives 0.5 mM Nice-Pak OEM Anion-BT 0.4 mM OFM Anion-BT None 8 mM hydroxyisobutyric acid 50 mM tetrabutyl ammonium hydroxide Analytes/Sample Organic/inorganic ions Organic/inorganic ions Metal ions Inorganic OTgMiic ions References Romano et al. (1991) Jones and Jandik (1992) Lu and Cassidy (1993) Audalovic et al. (1993)... 

Corresponding to the decomposition of boric acid, borate additives produce metaborate and then boron trioxide ... 

Examples of well-known PISs working under laser lights in this blue-green area include the Eosin/amine, Eosin/amine/bromo compound, ketocoumarin/amine/iodonium salt, thioxanthene dye/amine/iodonium salt, erythrosin/amine, julolidine dye/Cl-HABEthiol, cyanines and related compound/borate/additive systems, pyrromethine/amine/triazine or styryl naphtothiazole dye/Cl-HABEthiol systems and Cl-HABI-based systems. A lot of novel Dye/iodonium salts/silanes can also work (e.g. [XIA 15] see sections 1.3.5 and 1.3.6). 

Ha S-Y, Han J-G, Song Y-M, Chun M-J, Han S-1, Shin W-C, Choi N-S (2013) Using a lithium bis(oxalato) borate additive to improve electrochemical performance of high-voltage spinel LiNio.5Mn1.5O4 cathodes at 60 °C. Electrochim Acta 104 170-177. doi 10.1016/j. electacta.2013.04.082... 

A continuous process for the production of high dropping point lithium complex greases has been developed (13). Here, the conventional dibasic acid salt or the dibasic ester component is no longer used. These conventional components are substituted with a borated additive fed into the reactor downstream of the thickener formation zone. This substitution and process modification results in a significantly less problematic process and a substantial increase in production throughput (13). 

G.L. Fagan, Continuous lithium complex grease manufacturing process with a borated additive, US Patent 9157 045, assigned to Chevron U.S.A. Inc. (San Ramon, CA), October 13, 2015. 

The additives that can interact with anions are mainly electron acceptors. For example, the borates shown in Figure 9.20 can be used as additives to increase the ionic conductivity of the lithium salt by forming complexes with anions such as F and PFg". As a result, the solubility of lithium salt and the ionic conductivity of the prepared electrolyte are increased. Some values of ionic conductivities with borate additives are summarized in Table 9.6. Their electrochemical window is more than 5.0 V. 

In this work, we have evidenced the formation of a lamellar solid from the tribochemical reaction of a borated additive and a succinimide additive. The result is the formation of h-BN in the tribofilm. The tribofilm is mainly composed of an amorphous borate matrix containing highly-dispersed h-BN nanoparticles in the form of sheets less than 10 nm wide and 5 nm thick. The originality of this h-BN tribochemical reaction lies in the nature of the intermolecular reaction between the two additives. At the opposite, M0S2 formation fiom MoDTC is the result of intramolecular chemical reaction. 

Borated additives are commonly used in transmission oils for their excellent extreme-pressure action and good antiwear function. Many studies have shown that the action mechanism of borated additives is due to the formation of a protective film of borates by electrodeposition [4], [5]. On the other hand, nitrogenous additives (like succinimides) are often used as dispersants in most of lubricants. 

In this work, we investigate the formation of hexagonal boron nitride (h-BN) fiom the tribochemical reaction between a borated additive and a nitrogenous compound. We developed a multitechnique approach including X-Ray Photoelectron Spectroscopy (XPS), X-ray Absorption Near Edge Structure Spectroscopy (XANES), Electron Energy Loss Spectroscopy (EELS) and high resolution TEM (HRTEM). 

The base oil is a mineral oil containing a little amount of synthetic base. Two different additives are used a borated additive (potassium triborate) and a nitrogenous additive (succinimide). Three different formulations were compared the base oil alone (test A), the base oil containing the borated additive (test B) and finally the base oil in presence of the two additives (test C). At the end of the tests, the surfaces of wear scars were analysed by XPS and XANES and wear debris from the worn lubricant were analysed by EELS and HRTEM, respectively. 

The comparison of Bis and Nls XPS peaks for pure potassium borate additive, tribofilm of test C and pure h-BN is shown in. No BN bonding is detected in the spectra of pure potassium borate, only B-O (borate), N-C=0 and N-C-H (succinimide molecules) are detected. We deduce that h-BN is not present (or below 0,1 %) in the lubricant. 

ToF-SIMS spectra for pure potassium borate additive and h-BN powder are compared in Figure 6. Two different mass regions were observed the first... 

In this work, we have evidenced the formation of a lamellar solid fiom the tribochemical reaction of a borated additive and a succinimide additive. The result is the formation of h-BN in the tribofilm. Results can be summarized as followed ... 

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