- Characterisation and properties of new ionic liquids with the difluoromono[1,2-oxalato(2-)-O,O′]borate anion
-
Three ionic liquids with borate anions of low symmetry, tetraethylammonium difluoromono[1,2-oxalato(2-)-O,O′]borate, 1-ethyl-3-methylimidazolium difluoromono[1,2-oxalato(2-)-O,O′]borate, and 1-butyl-3-methylimidazolium difluoromono[1,2-oxalato(2-)-O,O′]borate were synthesised and characterised by physicochemical and electrochemical measurements including thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), cyclic voltammetry (CV), viscosity and conductivity measurements.
- Herzig, Tobias,Schreiner, Christian,Gerhard, Dirk,Wasserscheid, Peter,Gores, Heiner Jakob
-
-
Read Online
- Method for purifying lithium difluoroborate and lithium tetrafluoroborate mixed lithium salt and application thereof
-
The invention belongs to the technical field of lithium ion battery manufacturing, and discloses a method for purifying lithium difluoroborate and lithium tetrafluoroborate mixed lithium salt and application thereof. According to the preparation method of the high-purity mixed lithium salt with different proportions, industrial-grade lithium oxalate is used as a raw material, the mixed lithium salt with different molar proportions of lithium difluoroborate and lithium tetrafluoroborate is prepared through the processes of synthesis, concentration, auxiliary purification filter membrane purification and the like, and the mixed lithium salt can adapt to various electrolyte formulas, is used for manufacturing lithium ion batteries, and the production cost is reduced; meanwhile, the method provided by the invention avoids the tedious process of recrystallization and the solid-liquid separation operation after crystallization in the prior art, can improve the yield and purity of the product, and simplifies the technological process.
- -
-
Paragraph 0037-0119
(2021/04/10)
-
- Preparation method of lithium difluorooxalate borate
-
The invention discloses a preparation method of lithium difluorooxalate borate. The preparation method comprises the following steps: (1) placing anhydrous oxalic acid and anhydrous lithium chloride in a reaction vessel, adding an aprotic polar solvent to the reaction vessel under a nitrogen atmosphere, conducting reaction at 10-80 DEG C under a stirring condition for 1-12 h; reacting anhydrous oxalic acid with anhydrous lithium chloride to produce lithium hydrogen oxalate; (2) adding a boron trifluoride compound to the reaction vessel, continuing reaction for 1-12 h to produce lithium difluorooxalate borate; and (3) filtering a reaction solution after the reaction in step (2) at room temperature to remove solid raw materials which not completely react, and then concentrating and recrystallizing a filtrate obtained after filtration, then performing washing and filtration with a non-polar solvent, and finally, carrying out drying to obtain a solid lithium difluorooxalate borate product.The method is mild in reaction, simple in process, low in production cost, economical and environmentally friendly, can obtain high-purity lithium difluorooxalate borate, and is more suitable for industrial production.
- -
-
Paragraph 0031-0033
(2020/12/09)
-
- Preparation method for difluoro(oxalato)borate
-
The invention relates to the technical field of preparation of electrolyte additives for lithium batteries, and in particular relates to a simple, convenient, economical and easily-industrial preparation method for difluoro(oxalato)borate. The preparation method comprises the following steps: mixing dialkyl silyl oxalate, MBF4 and a solvent, performing a reaction to prepare a crude product, and performing post-treatment to obtain the difluoro(oxalato)borate, wherein M is any one selected from the group consisting of Li, Na, K, Rb and CS. According to the preparation method, halogen ions and other metal ions are not introduced in the technological process, the reaction and purification process is simple and convenient, and the product quality is easy to control; the conversion rate of the target product is higher, the reaction product is single, and almost no by-products are generated; and almost no three waste (wastewater, waste gas and solid waste) is generated in the implementation process, and the generated recovered solvent and filtered mother liquor can be reused after being distillated.
- -
-
Paragraph 0086-0091; 0139-0144; 0150-0159; 0163
(2020/01/12)
-
- Preparation method of lithium difluoro(oxalato)borate
-
The invention provides a preparation method of lithium difluoro(oxalato)borate (Li[B(C2O4)F2], LiDFOB). The method effectively recycles the by-product LiBF4, and avoids the waste of lithium atoms while improving the yield. The method utilizes the solubility difference of materials to directly filter out the by-product, and is simple in operation. The crude product is subjected to crystallization directly to obtain high purity LiDFOB, thus avoiding the product loss brought about by repeated recrystallization. The method has the advantages of cheap and easily available materials, simple reactionsteps and mild reaction conditions, and is suitable for large-scale industrial production.
- -
-
Paragraph 0045-0064
(2019/07/04)
-
- Method for synthesizing lithium difluorooxalate borate by one-pot method
-
The invention discloses a method for synthesizing lithium difluorooxalate borate by a one-pot method. The method is characterized by comprising the following steps: 1) preparation of lithium tetrafluoroborate: reacting lithium fluoride and boron trifluoride to prepare lithium tetrafluoroborate; 2) preparation of crude lithium difluorooxalate borate: reacting the obtained lithium tetrafluoroboratewith oxalic acid to obtain the crude lithium difluorooxalate borate; 3) preparation of electronic grade difluorooxalate borate: recrystallizing the crude lithium difluorooxalate borate by an organic solvent, washing and drying to obtain the electronic grade lithium difluorooxalate borate. The method for synthesizing the lithium difluorooxalate borate by the one-pot method has the beneficial effects that crystal obtained by the method disclosed by the invention has higher quality, the content is greater than 99.8%, and no sulfate ion exists.
- -
-
Paragraph 0024; 0025; 0026; 0028; 0031
(2019/02/06)
-
- Preparation method and purification method of compound comprising at least one cyclic ligand structure
-
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.
- -
-
Paragraph 0206-0209
(2019/03/29)
-
- Catalytic synthesis method of lithium difluoro(oxalato)borate
-
The invention relates to a catalytic synthesis method of lithium difluoro(oxalato)borate, belonging to the technical fields of new energy material preparation and chemical industry. The method comprises the following steps: (1) after all production reaction vessels are replaced with high-purity nitrogen, adding materials in a high-purity nitrogen protective atmosphere; (2) in a closed dry reactor, adding a certain amount of dry waterless lithium oxalate and a certain amount of boron trifluoride complex into an organic solvent reactor, and dissolving to prepare a solution; (3) adding a certain amount of catalyst, and sufficiently reacting at specified temperature to obtain a lithium difluoro(oxalato)borate-lithium tetrafluoroborate mixed solution; (4) adding a certain amount of waterless oxalic acid into the lithium difluoro(oxalato)borate-lithium tetrafluoroborate mixed solution, and sufficiently reacting under the control of specified temperature, specified pressure and a tail gas absorption solution, thereby obtaining the lithium difluoro(oxalato)borate solution. The catalytic synthesis method of lithium difluoro(oxalato)borate has the advantages of short reaction time, high product yield, low equipment investment, no pollution and wide application prospects, and is simple to operate.
- -
-
Paragraph 0023-0026
(2017/08/27)
-
- Process for synthesizing lithium difluoro(oxalate)borate from lithium bis(oxalate)borate
-
The invention discloses a process for synthesizing lithium difluoro(oxalate)borate from lithium bis(oxalate)borate. The process comprises the following steps: mixing lithium bis(oxalate)borate with a compound containing fluorine, boron and lithium; carrying out a reaction in a solvent system at a temperature of 0 to 150 DEG C and a reaction pressure of 101 kpa and 150 kpa to produce a product; and carrying out a reaction at a certain temperature and then carrying out crystallization and vacuum drying so as to obtain battery-grade lithium difluoro(oxalate)borate. The process provided by the invention is novel in process and mild in conditions and can prepare high-purity battery-grade lithium difluoro(oxalate)borate.
- -
-
Paragraph 0054; 0056; 0057; 0058
(2017/10/13)
-
- A oxalate two fluorine lithium borate electrolyte salt preparation method
-
The invention provides a preparation method of a high-purity lithium difluorooxalatoborate (LiODFB) electrolyte for a lithium ion battery. The preparation method comprises the following steps of firstly adding lithium oxalate and boron trifluoride diethyl ether according to a molar ratio being (1: 1) to (1: 3) into a dried ball-milling tank, carrying out ball-milling at a temperature of 30 DEG C-90 DEG C for 2 hours-24 hours; and then dissolving the ball-milled reaction product in an organic solvent at the temperature of 30-90 DEG C and filtering to remove a solid-phase byproduct and unreacted lithium oxalate to obtain a solution containing LiODFB, crystallizing at a low temperature of -20 DEG C to 10 DEG C to obtain LiODFB crystals and carrying out vacuum drying on the LiODFB crystals at 40 DEG C-100 DEG C for 10 hours-48 hours to obtain the purified LiODFB solid. The preparation method has the advantages of no strict requirements, such as high temperature resistance and high pressure resistance, simple operation and low investment in equipment and has very broad application prospects, and the product of which the purity is above 99.9% can be directly obtained by adopting the preparation method.
- -
-
Paragraph 0017; 0018; 0019; 00020; 0021
(2017/11/01)
-
- A two-fluorine oxalic acid acid lithium borate preparation method
-
The invention relates to a preparation method of lithium oxalyldifluoroborate. The preparation method comprises the steps that lithium bis(oxalato)borate and lithium fluoride are stirred to perform hybrid reaction in a non-aqueous solvent, wherein the molar ratio of the lithium bis(oxalato)borate to the lithium fluoride is within the range of (1:1.90)-(1:2.10), the reaction time lasts for 10-24 hours, and difluoro lithium bis(oxalato)borate and lithium oxalate are generated in the reaction, wherein the non-aqueous solvent is benzene, toluene or xylene, the reaction temperature is within the range of 50-85 DEG C, and the reaction time lasts for 12-16 hours. According to the invention, a technology line is unique, the lithium oxalyldifluoroborate is environment-friendly, the technology control range is wider, two resultants of the reaction are easy to separate, and electrolyte salt of which the quality satisfies the requirements of lithium batteries is easy to prepare. Because the content of chlorine compounds and the content of free acids are lower, the moisture content of the difluoro lithium bis(oxalato)borate solution prepared by the preparation method is controllable.
- -
-
Paragraph 0021; 0022; 0023; 0024
(2017/04/21)
-
- Difluoro oxalate process for the preparation of boric acid metal salt
-
The invention discloses a preparing method of difluoro oxalic acid boric acid metal salt, and belongs to the field of material chemistry. The method comprises the steps that boron compounds and oxalic acid ammonium salt compounds react with each other to compose dihalogenacid oxalic acid boric acid ammonium salt or double-alkyl oxygroup oxalic acid boric acid ammonium salt, then the dihalogenacid oxalic acid boric acid ammonium salt or the double-alkyl oxygroup oxalic acid boric acid ammonium salt reacts with fluorinated reagents to prepare difluoro oxalic acid ammonium salt, obtained products react with moderate MxCO3 or M(OH)y (when the M=Li, Na, K, Rb and Cs, x=2 and y=1; when the M=Mg and Zn, x=1 and y=2), and the difluoro oxalic acid boric acid metal salt is obtained, and the high-purity difluoro oxalic acid boric acid metal salt products obtained after recrystallization purification is conducted. The preparing method has the advantages of being simple in operation step, mild in preparing condition, high in purity and productivity, low in cost, suitable for large-scale industrialized production and the like.
- -
-
Paragraph 0026; 0027; 0029; 0030
(2017/02/17)
-
- Preparation method of lithium difluoro(oxalato)borate
-
The invention discloses a preparation method of lithium difluoro(oxalato)borate. The method comprises the following steps: adding lithium oxalate and anhydrous HF to a fluorine lining reaction kettle, and fully stirring to make lithium oxalate be fully dissolved in HF; introducing a boron trifluoride gas to the reaction kettle, controlling the flow velocity of boron trifluoride to be 0.5-2L/min, the reaction temperature to be 0-90DEG C, the reaction pressure to be 0-0.5MPa and the molar ratio of boron trifluoride to lithium oxalate to be 2.2-2:1, continuously stirring and reacting for 2-24h after introduction of the boron trifluoride gas is finished, and evaporating and crystallizing the above obtained reaction product o obtain crude lithium difluoro(oxalato)borate; and fast drying, adding an organic solvent, dissolving, filtering, and drying to obtain the lithium difluoro(oxalato)borate product, wherein the organic solvent adopts one or more of esters, ethers, alcohols and nitriles, the use amount of the organic solvent guarantees that lithium tetrafluoroborate can be completely dissolved in the organic solvent, and lithium difluoro(oxalato)borate cannot be completely dissolved in the organic solvent. The method is simple and practical, and can realize large-scale industrial production of lithium difluoro(oxalato)borate.
- -
-
Paragraph 0017
(2017/02/23)
-
- A synthetic method of electronic grade lithium difluoro(oxalato)borate
-
A synthetic method of electronic grade lithium difluoro(oxalato)borate is disclosed. The method includes directly reacting boron trifluoride and lithium oxalate in anhydrous hydrogen fluoride to generate the lithium difluoro(oxalato)borate. Firstly, high-purity lithium oxalate is dissolved into the anhydrous hydrogen fluoride the water content of which is lower than 20 ppm in a polytetrafluoroethylene reactor, a high-purity boron trifluoride gas is then fed to obtain a mixed product containing the lithium difluoro(oxalato)borate and lithium tetrafluoroborate, and the mixed product is crystallized, filtered, washed, dried and separated to obtain a high-purity electronic grade lithium difluoro(oxalato)borate product. The method is simple, reliable, high in product purity, low in product impurity contents and low in cost.
- -
-
Paragraph 0021-0030
(2017/01/12)
-
- METHOD FOR PRODUCING LITHIUM(OXALATO)BORATE
-
PROBLEM TO BE SOLVED: To provide a method for producing lithium(oxalato)borate that can shorten the processing time in comparison with the prior art. SOLUTION: There is provided a method for producing lithium(oxalato)borate characterized in mixing a lithium(oxalato)borate containing carbonic acid ester solution with a dialkyl ether or solvent represented by the following general formula (1) to precipitate lithium(oxalato)borate. (R1 each is independently selected from an alkyl group, an alkoxy group, and halogen, and n is an integer of 0 to 6.) COPYRIGHT: (C)2015,JPOandINPIT
- -
-
Paragraph 0041-0042
(2018/11/22)
-
- PURIFIED METAL COMPLEX HAVING OXALIC ACID AS LIGAND, AND METHOD FOR PRODUCING PURIFIED SOLUTION OF SAID METAL COMPLEX IN NON-AQUEOUS SOLVENT
-
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.
- -
-
Paragraph 0035; 0050; 0051
(2015/04/15)
-
- PROCESS FOR PREPARING METAL DIFLUOROCHELATOBORATES AND USE AS BATTERY ELECTROLYTES OR ADDITIVES IN ELECTROCHEMICAL CELLS
-
The invention relates to a process for preparing metal difluorochelatoborates, in which a metal bis(chelato)borate of the formula M[BL2] is reacted with boron trifluoride and a metal fluoride (MF) and/or a metal salt of the chelating ligand (M2L) where M+ is a monovalent cation selected from the group consisting of lithium, sodium, potassium and ammonium NR4+, where R═H, alkyl (C1 to C8) and L is a chelating agent having two terminal oxygen atoms and having the general formula (II), where: when m=1 and Y1 and Y2 together with C1 form a carbonyl group, n=0 or 1 and o=0 or 1 and R1 and R2 are each, independently of one another, H or alkyl having from one to eight carbon atoms (C1-C8) and Y3, Y4 are each, independently of one another, OR3 (R3═C1-C8-alkyl), then n or o≠1: p=0 or 1 and when n and o=0, p=1; or Y1, Y2, Y3, Y4 are each, independently of one another, OR3 (R3═C1-C8-alkyl), m=1, n=0 or 1, o=1 and p=0; or C2 and C3 are members of a 5- or 6-membered aromatic or heteroaromatic ring (with N, O or S as heteroelement) which can optionally be substituted by alkyl, alkoxy, carboxy or nitrile, where R1, R2, Y3 and Y4 are absent, m=0 or in the case of 1, Y1 and Y2 together with C1 form a carbonyl group and p is 0 or 1, in an organic, aprotic solvent.
- -
-
Paragraph 0051
(2014/09/30)
-
- Chloride-free method to synthesise new ionic liquids with mixed borate anions
-
A new chloride-free method to synthesize ionic liquids (ILs) with mixed borate anions was demonstrated. The anions used for the study were derived from [BF4]- by replacement of F- by mono- or bidentate ligands. The proposed method was depended on the type of ligand, while moisture exclusion and dried starting materials and solvent were used to minimize water content. The starting materials were heated to reflux in acetonitrile (MeCN) as solvent for monodentate ligands. The [BF 4]- compounds were diluted in MeCN to prevent the formation of bridged anions and the trime-thylsilyl compounds were added at a temperature of 45 °C. The proposed method opened new opportunities for preparing new ILs for different applications including their use as electrolytes in electrochemical double layer capacitors and lithium ion batteries.
- Schreiner, Christian,Amereller, Marius,Gores, Heiner J.
-
supporting information; experimental part
p. 2270 - 2272
(2009/10/23)
-
