- Preparation of LiBOB via rheological phase method and its application to mitigate voltage fade of Li1.16[Mn0.75Ni0.25]0.84O2 cathode
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Lithium bis(oxalato)borate (LiBOB) was synthesized via a novel rheological phase reaction method without any recrystallization procedure. The purity of the as-obtained LiBOB has been identified in comparison with the commercial sample and our sample prepared from solid-state reaction method. The results of XRD, ICP, and 11B NMR demonstrate that high pure LiBOB has been synthesized via rheological phase reaction method with significantly simplified synthetic process. Moreover, LiBOB sample has been investigated as electrolyte additive to improve the electrochemical performances of high-energy lithium-rich layered oxide. The cycling performances imply that 0.03 M and 0.05 M LiBOB additive can mitigate discharge voltage fade and enhance the cycle stability of Li1.16[Mn0.75Ni0.25]0.84O2 material. The CV, EIS and XPS data indicate that LiBOB oxidizes at ～4.3 V (vs. Li/Li+) on the cathode surface during the first charge to form a specific SEI layer with larger amount of organic species and fairly less content of LiF, which decreases the interfacial polarization and protects the active material from surface degradation, thereby mitigates the voltage-fade of Li-rich cathode.
- Lian, Fang,Li, Yang,He, Yi,Guan, Hongyan,Yan, Kun,Qiu, Weihua,Chou, Kuo-Chih,Axmann, Peter,Wohlfahrt-Mehrens, Margret
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- Structures of potassium, sodium and lithium bis(oxalato)borate salts from powder diffraction data
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The crystal structures of the alkali-metal bis(oxalato)borate salts A[B(C2O4)2] (A = K, Na, Li) have been determined ab initio using powder diffraction data obtained from a laboratory diffractometer. The K compound crystallizes in the orthorhombic space group Cmcm and its structure has been solved by direct methods applied to the integrated intensities from full pattern decomposition. The Na compound is isostructural with the K salt, while the crystal structure of the highly hydroscopic Li compound differs from the other two. It has an orthorhombic lattice, space group Pnma, and its structure was solved by the global optimization method using a parallel tempering approach. In the K and Na structures the metal ions and complex borate ions form chains with m2m symmetry. Metal-oxygen bonding between the chains links them into a layer and then a framework with square tunnels. The coordination number of both K and Na is eight. The Li compound also contains chains that have .m. symmetry and are bound together into a three-dimensional framework. The coordination polyhedron of the Li atom is a square pyramid with Li lying in its base. This square pyramidal coordination leads to its high reactivity with moisture to give Li[B(C2O4) 2]H2O with lithium in six coordination.
- Zavalij, Peter Y.,Yang, Shoufeng,Whittingham, M. Stanley
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Read Online
- Preparation method of lithium bis(oxalato)borate
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The invention discloses a preparation method of lithium bis(oxalato)borate. The preparation method mainly comprises: synthesizing a lithium bis(oxalato)borate crude product, concentrating, crystallizing and purifying, and specifically comprises the following steps: weighing and uniformly mixing elemental boron, lithium powder and anhydrous oxalic acid to obtain a raw material mixture; putting theraw material mixture into a ball mill, performing a normal-pressure reaction for 2-6 h, then adding an organic solvent, and performing wet grinding to obtain a solution containing the lithium bis(oxalato)borate crude product; and concentrating, crystallizing and filtering the solution containing the lithium bis(oxalato)borate crude product, and then drying to obtain the lithium bis(oxalato)borate.Production links are few, purification is convenient, the purity of the prepared lithium bis(oxalato)borate product can reach 99.99%, the moisture content is lower than 10 ppm, and the production requirements of lithium ion battery electrolytes are met.
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Paragraph 0058-0075
(2020/05/30)
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- Lithium bis(oxalate)borate preparation method
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The invention discloses a lithium bis(oxalate)borate preparation method, which comprises: adding a boron trifluoride dimethyl carbonate complex, lithium fluoride and an organic solvent into a reactionflask, mixing, heating while stirring, and carrying out a reaction; cooling the reaction solution to a room temperature, adding anhydrous oxalic acid into the reaction solution, heating under a stirring condition, adding silicon tetrachloride in a dropwise manner, continuously heating after the adding, and carrying out a reaction; filtering the reaction solution after the reaction, then concentrating the filtrate under a reduced pressure condition, adding an inert solvent into the filtrate, and carrying out stirring crystallization to obtain a lithium bis(oxalate)borate semi-finished product;and re-crystallizing and drying to obtain high-purity lithium bis(oxalate)borate. According to the invention, the method has the advantages of thorough reaction, reduction of the separation difficulty of the product and the by-product in the reaction process, improvement of the purity and the yield of the product, further reduction of the production cost, and improvement of the product quality.
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Paragraph 0014; 0028-0039
(2020/02/10)
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- Preparation method of bis(oxalate)borate
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The invention relates to the technical field of preparation of lithium battery electrolyte additives, in particular to a preparation method of bis(oxalate)borate. The preparation raw materials of thebis(oxalate)borate at least comprise dialkyl silicon oxalate and MBF4, wherein M is selected from any one of Li, Na, K, Rb and Cs. The bis(oxalate)borate is prepared from at least dialkyl oxalate estersil and MBF4, wherein M is selected from any one of Li, Na, K, Rb and Cs. According to the preparation method of the bis(oxalate)borate, the conversion rate of a target product is higher, the reaction product is single, and almost no by-product is generated; water and oxalic acid are not introduced in the technological process, the reaction and purification process is simple and convenient, and the product quality is easy to control; and almost no three wastes are generated in the implementation process, and a produced recovered solvent and a filtered mother liquor can be repeatedly used after distillation.
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Paragraph 0083; 0086-0093; 0134-0150; 0154
(2020/01/12)
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- Preparation method of lithium bis(oxalate)borate and lithium tetrafluoroborate
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The invention relates to a preparation method of electrolyte lithium salt used in the lithium ion battery industry, in particular to a preparation method of lithium bis(oxalate)borate and lithium tetrafluoroborate. The preparation method of the lithium bis(oxalate) borate and lithium tetrafluoroborate comprises the steps that (1) lithium difluorooxalate borate is dissolved in an inert atmosphere to form a solution; (2) an ionic coordination catalyst is added into the solution at the temperature of 0-105 DEG C and the pressure of 101-150 kpa to form a reaction product comprising the lithium bis(oxalate)borate and the lithium tetrafluoroborate. The preparation method of the lithium bis(oxalate) borate and lithium tetrafluoroborate has the advantages that the reaction rate is fast, the reaction condition is simple, the operation is convenient, and the yield is high; the raw material cost can be reduced, the material consumption and waste generation are reduced, the utilization rate, product yield and purity of raw materials are improved, and purification of the product is easier.
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Paragraph 0079-0093
(2019/06/27)
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- Preparation method and purification method of compound comprising at least one cyclic ligand structure
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The invention discloses a preparation method and a purification method of a compound comprising at least one cyclic ligand structure. The compound comprising the at least one cyclic ligand structure comprises 1-2 cyclic ligands in different structures, namely a cyclic ligand containing La and/or a cyclic ligand containing Lb, wherein the cyclic ligand containing La comprises one of sulfuryl (-SO2-), sulfinyl (-SO-) and carbonyl. The compound can serve as electrolyte lithium salt of a lithium ion battery independently, and is dissolved in an organic solvent for preparing an electrolyte solutionof the lithium ion battery; or, the compound and the lithium salt are dissolved in the organic solvent to prepare the electrolyte solution of the lithium ion battery; and the electrolyte solution canobviously improve internal resistance of the lithium ion battery and has an effect on cycle performance of the battery.
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Paragraph 0211-0214
(2019/03/29)
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- A process for preparing the lithium of the new method (by machine translation)
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The invention discloses a method for preparing the lithium of the new method, the non-aqueous phase synthesis process, to the oxalic acid, alkaline lithium compounds and three (three hydrocarbyl silicon-based) boric acid ester as the raw material, according to the contained in the raw material of the oxalate ion, lithium ion and elemental molar ratio calculation, the oxalic acid and alkaline lithium compound is added non-proton, non-reactive solvent, dissolve and dehydration, then adding three (three hydrocarbyl silicon-based) borate, after reaction, distillation for removing by-product and solvent, pair of oxalic acid to obtain crude lithium borate, re-purification, obtained lithium for lithium battery. The invention through the non-aqueous phase synthesis process to prepare the lithium, easy dehydration and purification, the reaction product contains very little moisture, even free of water, so as to maximally lowering the moisture content in the product, effectively solve the influence of moisture to the purification, simplifies the preparation process, improves the yield of the product, the resulting lithium high purity, more suitable for industrial production. (by machine translation)
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Paragraph 0033-0034; 0039-0040
(2019/02/13)
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- Synthetic Method of Lithium bisoxalatoborate
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A synthesis method of lithium bisoxalato borate (LiBOBOB) is. The synthesis of lithium bisoxalato borate, LiBOBOB, is a method of synthesizing lithium bisoxalato borate (LiBOB) using a polar solvent having a higher boiling point than water to synthesize lithium bisoxalato borate. LiBOBOB, LiBOB) and a Lithium bisbisbisbisbisate (LiBOB). To the invention, the invention resides in the invention. In order to synthesize lithium bisoxalato borate (LiBOB), a polar solvent having a higher boiling point than water is used to completely remove water and remove impurities from the reaction during the reaction, thereby simplifying) the synthesis process of the compound and high-purity lithium bisoxalato borate (LiBOB). (LiBOB) (can be synthesized by high yield/high purity lithium bisoxalato borate. (by machine translation)
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Paragraph 0032; 0067-0099
(2019/10/17)
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- Preparation method and application of lithium bis(oxalato)borate
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The invention discloses a preparation method of lithium bis(oxalato)borate. The whole synthesis process is conducted in solvent, reaction steps are few, reaction, separation and purification are completed in one step, and product purity is high. The defect that solid-phase reaction oxalic acid is prone to sublimation is overcome, and by-products of the whole process method include H2O and CO2, are harmless to the environment and can not cause secondary pollution. The I-type solvent and the II-type solvent can be used as reaction solvent, can also be used as purification solvent and can be recycled. Lithium bis(oxalato)borate is suitable for being used as lithium ion battery electrolyte salt.
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Paragraph 0037; 0038
(2016/12/01)
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- PURIFIED METAL COMPLEX HAVING OXALIC ACID AS LIGAND, AND METHOD FOR PRODUCING PURIFIED SOLUTION OF SAID METAL COMPLEX IN NON-AQUEOUS SOLVENT
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The present invention provides a purified metal complex having oxalic acid as a ligand and a method for industrially producing a purified non-aqueous solvent solution of the metal complex at low cost. In the method of the present invention, oxalic acid contained in a non-aqueous solvent solution of a metal complex having oxalic acid as a ligand is decomposed by a reaction with a thionyl halide in a non-aqueous solvent, and the decomposition product of the reaction and the unreacted thionyl halide are removed by deaeration.
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Paragraph 0035; 0044; 0045
(2015/04/15)
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- Electrolytic salts for lithium batteries
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Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.
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- Ionic liquids of chelated orthoborates as model ionic glassformers
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Ionic liquids based on various chelated orthoborate anions of different N-containing onium cations have been synthesized using an economic synthesis strategy. Most orthoborates do not crystallize. They are found to have much higher glass transition temperatures and room-temperature viscosities than those with perfluorinated anions such as TFSI-, BF4-, and CF3SO3- (Tf-), as predicted from anion polarizability arguments. The ambient conductivities of the new ionic liquids are low relative to those with perfluorinated anions. The transport properties all show that cohesion in these liquids increases, and ionic mobilities decrease, as anion size increases, implying that van der Waals interactions, not Coulomb interactions, have become the controlling influence. In view of their resistance to crystallization, the large range of temperature over which these liquids can be studied, their hydrophobic properties, and their high fragilities, these liquids may provide good model systems for fundamental liquid state investigations and interesting solvents for large-molecule dissolution.
- Xu, Wu,Wang, Li-Min,Nieman, Ronald A.,Angell, C. Austen
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p. 11749 - 11756
(2007/10/03)
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