- 7Li NMR studies on complexation reactions of lithium ion with cryptand C211 in ionic liquids: Comparison with corresponding reactions in nonaqueous solvents
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7Li NMR spectra of DEME-TFSA [DEME = N,N-diethyl-N-methyl-N-(2- methoxyethyl)ammonium; TFSA = bis(trifluoromethanesulfonyl)amide], EMI-TFSA (EMI = 1-ethyl-3-methylimidazolium), MPP-TFSA (MPP = N-methyl-N-propylpyridinium), DEME-PFSA [PFSA = bis(pentafluoroethanesulfonyl)amide], and DEME-HFSA [HFSA = bis(heptafluoropropanesulfonyl)amide] ionic liquid (IL) solutions containing LiX (X = TFSA, PFSA, or HFSA) and C211 (4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5] eicosane) were measured at various temperatures. As a result, it was found that the uncomplexed Li(I) species existing as [Li(X)2]- in the present ILs exchange with the complexed Li(I) ([Li?C211]+) and that the exchange reactions proceed through the bimolecular mechanism, [Li?C211]+ + [*Li(X)2]- = [*Li?C211]+ + [Li(X)2]-. Kinetic parameters [ks/(kg m-1 s-1) at 25 °C, ΔH?/(kJ mol-1), ΔS?/ (J K-1 mol-1)] are as follows: 5.57 × 10 -2, 69.8 ± 0.4, and -34.9 ± 1.0 for the DEME-TFSA system; 5.77 × 10-2, 70.6 ± 0.2, and -31.9 ± 0.6 for the EMI-TFSA system, 6.13 × 10-2, 69.0 ± 0.3, and -36.7 ± 0.7 for the MPP-TFSA system; 1.35 × 10-1, 65.2 ± 0.5, and -43.1 ± 1.4 for the DEME-PFSA system; 1.14 × 10-1, 64.4 ± 0.3, and -47.1 ± 0.6 for the DEME-HFSA system. To compare these kinetic data with those in conventional nonaqueous solvents, the exchange reactions of Li(I) between [Li?C211]+ and solvated Li(I) in N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) were also examined. These Li(I) exchange reactions were found to be independent of the concentrations of the solvated Li(I) and hence proposed to proceed through the dissociative mechanism. Kinetic parameters [ks/s -1 at 25 °C, ΔH?/(kJ mol-1), ΔS?/(J K-1 mol-1)] are as follows: 1.10 × 10-2, 68.9 ± 0.2, and -51.3 ± 0.4 for the DMF system; 1.13 × 10-2, 76.3 ± 0.3, and -26.3 ± 0.8 for the DMSO system. The differences in reactivities between ILs and nonaqueous solvents were proposed to be attributed to those in the chemical forms of the uncomplexed Li(I) species, i.e., the negatively charged species ([Li(X)2]-) in ILs, and the positively charged ones ([Li(solvent)n]+) in nonaqueous solvents.
- Shirai, Atsushi,Ikeda, Yasuhisa
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- The electrode potentials of the Group i alkali metals in the ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide
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The redox couples M/M+ of the Group I alkali metals Lithium, Sodium, Potassium, Rubidium and Caesium have been extensively investigated in a room temperature ionic liquid (IL) and compared for the first time. Cyclic voltammetric experiments in
- Wibowo, Rahmat,Aldous, Leigh,Jones, Sarah E. Ward,Compton, Richard G.
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- METHOD FOR PRODUCING PHOSPHORYL IMIDE SALT, METHOD FOR PRODUCING NONAQUEOUS ELECTROLYTE SOLUTION CONTAINING SAID SALT, AND METHOD FOR PRODUCING NONAQUEOUS SECONDARY BATTERY
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To provide a method for producing a phosphoryl imide salt represented by the following general formula (1) at a satisfactory yield by cation exchange. The method comprises the step of performing cation exchange by bringing a phosphoryl imide salt represented by the following general formula (2) into contact with a cation exchange resin having M1 n+ or a metal salt represented by the general formula (4) in an organic solvent having a water content of 0.3% by mass or less.
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Paragraph 0282; 0294
(2020/05/02)
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- Preparation method of lithium bis (trifluoromethanesulfonyl) imide
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The invention provides a preparation method of lithium bis (trifluoromethanesulfonyl) imide. The method mainly comprises the following steps: neutralizing trifluoromethanesulfonamide with an alkali metal lithium salt to obtain a lithium trifluoromethanesulfonamide salt, the reaction yield is up to 99%, and reaction can be completed after 20 minutes of quick reaction; reacting the obtained lithiumtrifluoromethanesulfonamide with trifluoromethanesulfonyl chloride under the catalytic action of lithium carbonate, saccharin lithium, lithium oxalate and other lithium salts to obtain lithium bis (trifluoromethanesulfonyl) imide with the purity of 99.9% and the yield of higher than 95%. The preparation method of the lithium bis (trifluoromethanesulfonyl) imide is more convenient, safer, low in cost and free of metal impurities.
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Paragraph 0038-0046
(2021/01/11)
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- New process of bis-trifluoro sulfonimide salt
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The invention provides a preparation method of a bis-trifluoro sulfonimide salt. The method comprises the following steps of S1, preparing corresponding N-alkyl-substituted bis-trifloromethane sulfonimide with primary amine and trifluoromethyl sulfonic anhydride; S2, reacting the N-alkyl-substituted bis-trifloromethane sulfonimide with a salt to obtain a crude product; S3, crystallizing the crudeproduct and then drying the crude product in vacuum to obtain the bis-trifloromethane sulfonimide salt. The method has the advantages that N-alkyl-substituted bis-trifloromethane sulfonimide is stablein property and does not generate corrosive substances in a whole reaction process, three wastes are hardly generated, the method is suitable for large-scale production, the high-purity battery-gradebis-trifloromethane sulfonimide salt can be obtained, and a high implementation value and considerable social and economic benefits are acquired.
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Paragraph 0062; 0063; 0066; 0067
(2019/06/12)
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- Preparation method of lithium bis(trifluoromethanesulphonyl)imide salt
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The invention provides a preparation method of lithium bis(trifluoromethanesulphonyl)imide salt. The preparation method is characterized by comprising steps as follows: trifluoromethane gas is introduced into a non-polar solvent solution of lithium alkylide at low temperature under anhydrous and nitrogen protective conditions and subjected to a reaction, trifluoromethyl lithium is prepared, afterthe reaction, a lithium bis(fluorosulfonyl)imide solution is slowly dropwise added to the trifluoromethyl lithium solution at the low temperature, white solids can be separated out in a dropwise adding process, a reaction solution is filtered after dropwise addition is finished, a filtrate is evaporated under reduced pressure to be dry, white solid wet salt is obtained and subjected to vacuum drying, and lithium bis(trifluoromethanesulphonyl)imide salt is obtained. The preparation method has the advantages as follows: bis(trifluoromethanesulphonyl)imide is synthesized with a one-pot method, compared with a traditional method, a process route is greatly simplified, separating difficulty of a product and a byproduct in a reaction process is reduced, product purity is improved, so that production cost is further reduced, product performance and cost competitiveness are improved, and feasible technical support is provided for large-scale industrial production.
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Paragraph 0033; 0034
(2019/03/08)
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- Preparation method of LiN(CF3SO2)2 salt
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The invention discloses a preparation method of LiN(CF3SO2)2 salt. The preparation method comprises the following steps: benzene methanamine is dissolved in an organic solvent and subjected to a sulfonamide reaction with trifluoromethyl sulfonyl chloride or trifluoromethyl sulfonyl fluoride, benzyl bis(trifluoromethyl sulfamide) is obtained and reduced, and bis(trifluoromethyl sulfamide) is obtained; the obtained bis(trifluoromethyl sulfamide) and resin lithium are subjected to ion exchange in an anhydrous solvent, and a final product LiN(CF3SO2)2 salt is obtained. According to the method, raw materials are low in price and easy to obtain, reaction procedures are simple, the yield is high, nearly no pollution is caused, rigid and dangerous reaction conditions are avoided, the product is easy to purify, and the method is suitable for large-scale production in China.
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Paragraph 0047; 0049; 0050; 0053; 0054
(2018/02/04)
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- A method of preparing lithium imide fluorine sulfuryl
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The invention relates to a method for preparing fluorine sulfimide lithium and belongs to the field of fine chemical industries. The method comprises the steps as follows: lithium salt and deionized water are prepared into a turbid liquid with the mass concentration of the lithium salt in a range of 20-50% in a reaction still, a refined fluorine sulfimide acid solution is added dropwise to obtain a reaction solution under the condition of stirring, the mass content of the deionized water in the fluorine sulfimide acid solution is in a range of 5-20%, the reaction temperature is in a range of 50-150 DEG C, and the reaction is stopped when the pH value of the reaction solution is in a range of 6-8. Non-vacuum drying is performed on the reaction solution firstly, and when the mass content of the deionized water is lower than or equal to 0.5%, vacuum drying is performed. The method is easy to operate, higher in process safety and capable of effectively improving the purity of products and satisfying requirements of lithium battery industries for the high purity.
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Paragraph 0048-0049; 0053-0054
(2017/01/19)
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- METHOD FOR PREPARING A SULFONIMIDE COMPOUND AND SALTS THEREOF
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The present invention relates to a method for preparing an aqueous sulfonimide compound of the formula (Rf1—SO2) (Rf2—SO2)NH, wherein Rf1et Rf2 are independently selected from the group comprising: a fluorine atom and groups having 1 to 10 carbon atoms selected from the perfluoroalkyl, fluoroalkyl, fluoroalkenyl and fluoroallyl groups, from a mixture M1 including (Rf1—SO2)(Rf2—SO2)NH, Rf1SO2H and/or Rf2SO2H, Rf1SO2NH2 and/or Rf2SO2NH2, characterized in that said method includes an oxidation step of said mixture M1 using an oxidizing agent in order to obtain a mixture M2 including (Rf1—SO2)(Rf2—SO2)NH, Rf1SO3H and/or Rf2SO3H, and Rf1SO2NH2 and/or Rf2SO2NH2.
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Paragraph 0370; 0371
(2015/07/27)
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- The method for manufacturing the same and sulfoneimido compd. (by machine translation)
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The present invention relates to a method for preparing an aqueous sulfonimide compound of the formula (Rf1—SO2) (Rf2—SO2)NH, wherein Rf1et Rf2 are independently selected from the group comprising: a fluorine atom and groups having 1 to 10 carbon atoms selected from the perfluoroalkyl, fluoroalkyl, fluoroalkenyl and fluoroallyl groups, from a mixture M1 including (Rf1—SO2)(Rf2—SO2)NH, Rf1SO2H and/or Rf2SO2H, Rf1SO2NH2 and/or Rf2SO2NH2, characterized in that said method includes an oxidation step of said mixture M1 using an oxidizing agent in order to obtain a mixture M2 including (Rf1—SO2)(Rf2—SO2)NH, Rf1SO3H and/or Rf2SO3H, and Rf1SO2NH2 and/or Rf2SO2NH2.
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Paragraph 0316; 0317
(2017/01/02)
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- A simple access to metallic or onium bistrifluoromethanesulfonimide salts
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Numerous salts of the (CF3SO2)2N- anion, called TFSI, were prepared according to an original one-pot procedure. First, N-benzyl trifluoromethanesulfonimide (N-benzyl triflimide) was treated with ethanol to form
- Arvai, Roman,Toulgoat, Fabien,Langlois, Bernard R.,Sanchez, Jean-Yves,Médebielle, Maurice
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experimental part
p. 5361 - 5368
(2009/12/01)
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- MOLTEN SALT COMPOSITION AND USE THEREOF
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Molten salt compositions comprising two or more types of molten salts (MTFSI) containing imido anion (TFSI) as an anion and alkali metal (M) as a cation exhibit a lowered electrolyte melting point and an enlarged operating temperature range as compared with those of single salts. Therefore, various advantages, such as enlarging of the range of material choice in the use in battery, etc., can be brought about.
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Page/Page column 15
(2008/06/13)
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- Perfluoroalkanesulfonylimids and their lithium salts: Synthesis and characterisation of intermediates and target compounds
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ECF processes have been extensively experienced and developed since early 1970s at the Fluorine Chemistry Laboratory of Padua University: several classes of perfluorinated inert and functional compounds have been obtained, in particular perfluoro heterocyclics and perfluorinated acid fluorides.Recently the demand for electrolyte salts, applied in lithium batteries, drove our interest to investigate on the perfluoroalkanesulfonylimides.A series of the perfluoroalkanesulfonylfluoride precursors has been obtained by ECF and their metathesis to the related imides and lithium salts has been investigated.A number of representative products has been obtained and characterized in their structure and ionic conductivity.
- Conte, Lino,Gambaretto, Gian Paolo,Caporiccio, Gerardo,Alessandrini, Fabrizio,Passerini, Stefano
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p. 243 - 252
(2007/10/03)
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- Methods of purifying lithium salts
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Provided are methods of purification of an organic lithium salt comprising the steps of: (a) dissolving an impure organic lithium salt in a solution comprising an organic complexing solvent; (b) crystallizing from said solution a solid solvate complex comprising said lithium salt and said organic complexing solvent; (c) separating said solid solvate complex from said solution; (d) dissociating said solid solvate complex to yield: (i) said lithium salt in a solid form, and, (ii) a volatile composition comprising said organic complexing solvent; and, (e) removing said volatile composition to yield said lithium salt in a solid form of purity greater than the purity of said impure lithium salt. The present invention also pertains to electrolytes for electric current producing cells comprising such purified lithium salts.
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- Process for synthesis of sulfonylimides
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The invention relates to a process for the synthesis of sulfonylimides. The process for the synthesis of sulfonylimides of the general formula M[RSO2)2 N]y, in which M represents a metal chosen from alkali metals, alkaline earth metals, rare earths, Al, Sc, Y and Th, R represents a monovalent radical chosen from linear or branched aliphatic radicals having 1 to 8 carbon atoms, alicyclic radicals having 3 to 8 carbon atoms, aryl radicals having 3 to 8 carbon atoms, and y is a number equal to the valence of M, is characterized in that an ionic nitride of the formula M3 Ny, in which M and y have the meaning given above, is reacted with a sulfonyl halide of the formula RSO2 X, in which R has the meaning given above, and X is chosen from F or Cl, in an aprotic polar solvent.
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