Search

CN-122010807-A - Preparation method of negative charge highly delocalized sulfimide alkali metal salt

CN122010807ACN 122010807 ACN122010807 ACN 122010807ACN-122010807-A

Abstract

The invention provides a synthesis method of negative charge highly delocalized sulfimide alkali metal salt { [ (R 3 SO 2 )(R 2 (R 1 SO 2 N) SO) N ] M, M=Li, na, K, rb or Cs, wherein alkyl (S-alkyl sulfimide) potassium (or rubidium and cesium) sulfinate and an N-fluorine electrophile are utilized to carry out an oxidative fluorination reaction to synthesize alkyl (S-alkyl sulfimide) sulfonyl fluoride, and the yield is 70-90%; the obtained alkyl (S-alkyl sulfonyl) sulfonyl fluoride and sulfonamide or alkali metal salt thereof containing substituent R 3 undergo nucleophilic substitution reaction, and the product is purified to obtain high-purity negative-charge highly-delocalized sulfonyl imide alkali metal salt, which has the characteristics of simple operation, low raw material price, easy separation and purification of the product, suitability for industrialized mass production and the like, and the prepared negative-charge highly-delocalized sulfonyl imide alkali metal salt has high chemical stability and good solubility, and is a preferred electrolyte material for realizing high specific energy power and energy storage batteries.

Inventors

  • ZHANG HENG
  • WANG XINGXING
  • LIU DONG
  • ZHOU ZHIBIN
  • FENG WENFANG

Assignees

  • 华中科技大学

Dates

Publication Date
20260512
Application Date
20241111

Claims (11)

  1. 1. A negatively charged highly delocalized alkali metal sulfonimide salt having the structure of the following formula (I), In formula (I): m= Li, na, K, rb or Cs; The substituents R 1 、R 2 、R 3 each independently have the meaning set forth in any one of ① to ⑧ below, and R 1 、R 2 and R 3 can be the same or different: ① Is perfluoroalkyl C m F 2m+1 , wherein m is 0 or a positive integer from 1 to 8, preferably m is a positive integer from 1 to 4; ② Is perfluoroalkoxy C m F 2m+1 O, wherein m is a positive integer from 1 to 8, preferably m is a positive integer from 1 to 4; ③ Fluoroalkyl H (CF 2 CF 2 O) m CF 2 CF 2 or F (CF 2 CF 2 O) m CF 2 CF 2 , wherein m is 0 or a positive integer from 1 to 6; ④ Is a hydrocarbon alkyl C m H 2m+1 , wherein m is a positive integer from 1 to 10, preferably m is a positive integer from 1 to 4; ⑤ Is a hydrocarbon alkoxy group C m H 2m+1 O, wherein m is a positive integer from 1 to 10; ⑥ Is a partially halogenated alkyl group, i.e. C m X n H 2m+1-n , wherein X=F, cl, br or I, n≤2m+1, m is a positive integer from 1 to 10, preferably CF 2 H、CH 2 F、CF 3 CH 2 、(CF 3 ) 2 CH、CCl 2 H、CH 2 Cl or CCl 3 CH 2 ; ⑦ Is a partially haloalkoxy group, i.e., C m X n H 2m+1-n O, wherein X=F, cl, br or I, n≤2m+1, m is a positive integer from 1 to 10, preferably CF 3 CH 2 O、(CF 3 ) 2 CHO、ClCH 2 O、Cl 2 CHO or CCl 3 CH 2 O; ⑧ Is an unsaturated double bond containing group including, but not limited to, the unsaturated double bond containing group ：CH 2 ＝CH–C 6 H 4 、CH 2 ＝CH–C 6 H 3 (CH 3 )、CH 2 ＝CH–C 6 H 3 Cl、CH 2 ＝CH–C 6 H 3 F、CH 2 ＝CH–COOCH 2 、CH 2 ＝C(CH 3 )–COOCH 2 、CH 2 ＝CH–COOCH 2 CH 2 、CH 2 ＝C(CH 3 )– described below COOCH 2 CH 2 、CH 2 ＝CH–COOCH 2 CH 2 CH 2 、CH 2 ＝C(CH 3 )–COOCH 2 CH 2 CH 2 、CH 2 ＝CH– COOCH 2 CH 2 CH 2 CH 2 、CH 2 ＝C(CH 3 )–COOCH 2 CH 2 CH 2 CH 2 ; Preferably CH 2 ＝CH–C 6 H 4 , CH 2 ＝C(CH 3 )–COOCH 2 CH 2 or CH 2 ＝C(CH 3 )–COOCH 2 CH 2 CH 2 .
  2. 2. The method for synthesizing the negative charge highly delocalized alkali metal sulfonimide salt according to claim 1, comprising the steps of: Step one, in a nonaqueous solvent, performing oxidative fluorination reaction on alkali metal salt of alkyl (S-alkylsulfonimide) sulfinic acid and an N-fluorine electrophile to generate alkyl (S-alkylsulfonimide) sulfonyl fluoride, wherein the structure of the alkyl (S-alkylsulfonimide) sulfonyl fluoride is shown as a formula (II): in formula (II): R 1 、R 2 each independently has the meaning set forth in any one of ① to ⑧ below, and R 1 、R 2 may be the same or different: ① Is perfluoroalkyl C m F 2m+1 , wherein m is 0 or a positive integer from 1 to 8, preferably m is a positive integer from 1 to 4; ② Is perfluoroalkoxy C m F 2m+1 O, wherein m is a positive integer from 1 to 8, preferably m is a positive integer from 1 to 4; ③ Fluoroalkyl H (CF 2 CF 2 O) m CF 2 CF 2 or F (CF 2 CF 2 O) m CF 2 CF 2 , wherein m is 0 or a positive integer from 1 to 6; ④ Is a hydrocarbon alkyl C m H 2m+1 , wherein m is a positive integer from 1 to 10, preferably m is a positive integer from 1 to 4; ⑤ Is a hydrocarbon alkoxy group C m H 2m+1 O, wherein m is a positive integer from 1 to 10; ⑥ Is partially haloalkyl, i.e. C m X n H 2m+1-n , wherein X=F, cl, br or I, n≤2m+1, m is a positive integer from 1 to 10, preferably CF 2 H、CH 2 F、CF 3 CH 2 、(CF 3 ) 2 CH、CCl 2 H、CH 2 Cl or CCl 3 CH 2 ; ⑦ Is a partially haloalkoxy group, i.e. C m X n H 2m+1-n O, wherein X=F, cl, br or I, n≤2m+1, m is a positive integer from 1 to10, preferably CF 3 CH 2 O,(CF 3 ) 2 CHO,ClCH 2 O,Cl 2 CHO or CCl 3 CH 2 O; ⑧ Is an unsaturated double bond containing group including, but not limited to, unsaturated double bond containing group ：CH 2 ＝CH–C 6 H 4 、CH 2 ＝CH–C 6 H 3 (CH 3 )、CH 2 ＝CH–C 6 H 3 Cl、CH 2 ＝CH– described below C 6 H 3 F、CH 2 ＝CH–COOCH 2 、CH 2 ＝C(CH 3 )–COOCH 2 、CH 2 ＝CH–COOCH 2 CH 2 、CH 2 ＝C(CH 3 )–COOCH 2 CH 2 、CH 2 ＝CH–COOCH 2 CH 2 CH 2 、CH 2 ＝C(CH 3 )–COOCH 2 CH 2 CH 2 、CH 2 ＝CH– COOCH 2 CH 2 CH 2 CH 2 、CH 2 ＝C(CH 3 )–COOCH 2 CH 2 CH 2 CH 2 ; Preferably CH 2 ＝CH–C 6 H 4 , CH 2 ＝C(CH 3 )–COOCH 2 CH 2 or CH 2 ＝C(CH 3 )–COOCH 2 CH 2 CH 2 . Step two, taking inorganic base or organic base as an acid binding agent, carrying out nucleophilic substitution reaction on the alkyl (S-alkylsulfonyl imino) sulfonyl fluoride prepared in the step one and sulfonamide with a structural formula of R 3 SO 2 NH 2 or alkali metal salt thereof (R 3 SO 2 NHM), purifying a reaction product to obtain negative charge highly delocalized sulfonyl imide salt with a hydrogen-containing proton with a structure shown as a formula (III), wherein R 3 in R 3 SO 2 NH 2 and R 3 SO 2 NHM has the same meaning as R 3 in the formula (I) in claim 1, and M in R 3 SO 2 NHM is Li, na, K, rb or Cs; In formula (III): C # -is a cation containing a hydrogen proton; r 1 、R 2 、R 3 has the same meaning as R 1 、R 2 、R 3 described in claim 1. And thirdly, carrying out double decomposition reaction on the negative charge highly delocalized sulfimide salt containing hydrogen protons (formula (III)) obtained in the step two and an alkali metal oxygen-containing compound or an oxygen-containing acid salt, and purifying a reaction product to obtain the negative charge highly delocalized sulfimide alkali metal salt with the structure shown in the formula (I) in claim 1.
  3. 3. The method according to claim 2, wherein the N-fluoro electrophile in the first step is one of N-fluoro succinimide (NFS), N-fluoro phthalimide (NFOBS), N-fluoro pyridine salt (NFPY), 1-chloromethyl-4-fluoro-1, 4-diazabicyclo [2.2.2] octane bis (tetrafluoroborate) salt (F-TEDA), N-fluoro bis-benzenesulfonamide (NFSI), N-fluoro bis-trifluoromethylsulfonamide (F-TFSI), or a mixture of two or more thereof.
  4. 4. The synthesis according to claim 2, wherein in step one the molar ratio of alkali metal salt of alkyl (S-alkylsulfonimide) sulfinic acid to N-fluoro electrophile calculated is from 100:20 to 100:500, preferably from 100:50 to 100:300.
  5. 5. The method according to claim 2, wherein the nonaqueous solvent in the first step is one or two or more of butyl acetate, N-dimethylaniline, dimethylamine, ethylene glycol dimethyl ether, diethyl ether, methyl tert-butyl ether, ethyl acetate, tetrahydrofuran, 1, 2-dichloroethane, acetone, butanone, 4-methyl-2-pentanone, ethanol, ethylene glycol, isopropanol, 1, 2-propanediol, nitromethane, nitroethane, hexamethylphosphoric triamide, acetonitrile, propionitrile, succinonitrile, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, N-methylformamide, sulfolane, 1, 3-Dimethylpropyleneurea (DMPU), 1, 3-dimethyl-2-imidazolidinone (DMEU), preferably one or two or more of acetonitrile, dichloromethane, diethyl ether, tetrahydrofuran.
  6. 6. The synthetic method according to claim 2, wherein the reaction temperature of the reaction in step one is a constant temperature of between-20 ℃ and 80 ℃, preferably a reaction temperature interval of between 10 ℃ and 60 ℃, and wherein the reaction time of the reaction in step one is between 0.5 hours and 48 hours, preferably between 0.5 hours and 10 hours.
  7. 7. The method according to claim 2, wherein the organic base used as the acid-binding agent in the second step is one or two or more of imidazole, 1-methylimidazole, triazole, pyridine, 2, 6-lutidine, triethylamine, diisopropylethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), hexamethyldisilazane potassium amide, hexamethyldisilazane sodium amide, hexamethyldisilazane lithium amide, tetramethylpiperidine sodium, tetramethylpiperidine lithium, or a mixture of two or more of them, and preferably one or two or more of triethylamine, imidazole, 1-methylimidazole, pyridine, 2, 6-lutidine, hexamethyldisilazane sodium amide.
  8. 8. The method according to claim 2, wherein the inorganic base used as the acid-binding agent in the second step is one or two or more of potassium phosphate (K 3 PO 4 ), sodium phosphate (Na 3 PO 4 ), lithium phosphate (Li 3 PO 4 ), dipotassium hydrogen phosphate (K 2 HPO 4 ), disodium hydrogen phosphate (Na 2 HPO 4 ), dilithium hydrogen phosphate (Li 2 HPO 4 ), potassium dihydrogen phosphate (KH 2 PO 4 ), sodium dihydrogen phosphate (NaH 2 PO 4 ), lithium dihydrogen phosphate (LiH 2 PO 4 ), sodium thiosulfate (Na 2 S 2 O 3 ) and potassium thiosulfate (K 2 S 2 O 3 ), and preferably one or two or more of potassium phosphate, lithium phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate and tripotassium phosphate.
  9. 9. The synthetic method according to claim 2, wherein the reaction temperature of the reaction in step two is a constant temperature of between-20 ℃ and 150 ℃, preferably a reaction temperature interval of between 0 ℃ and 100 ℃, and the reaction time of the reaction in step two is between 4 hours and 24 hours, preferably a reaction time of between 6 hours and 12 hours.
  10. 10. The method according to claim 2, wherein the alkali metal oxygen-containing compound in the third step is lithium oxide (Li 2 O), sodium oxide (Na 2 O), potassium oxide (K 2 O), lithium hydroxide (LiOH), One or two or more of sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH) and cesium hydroxide (CsOH), wherein the alkali metal oxysalt in the third step is lithium bicarbonate (LiHCO 3 ), sodium bicarbonate (NaHCO 3 ), potassium bicarbonate (KHCO 3 ), rubidium bicarbonate (RbHCO 3 ), cesium bicarbonate (CsHCO 3 ), lithium carbonate (Li 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), rubidium carbonate (Rb 2 CO 3 ), cesium carbonate (Li 2 CO 3 ), lithium hydrogen phosphate (LiH 2 PO 4 ), sodium hydrogen phosphate (NaH 2 PO 4 ), potassium hydrogen phosphate (KH 2 PO 4 ), lithium phosphate (Li 3 PO 4 ), sodium phosphate (Na 3 PO 4 ), one or two or more of potassium phosphate (K 3 PO 4 ).
  11. 11. The synthetic method according to claim 2, wherein the purification in the second step and/or the third step is specifically performed by filtering the obtained reaction product through a decompression funnel, washing the reaction product with a reaction solvent for a plurality of times, collecting the filtrate, concentrating the filtrate under reduced pressure, and drying the filtrate under vacuum to obtain the target product.

Description

Preparation method of negative charge highly delocalized sulfimide alkali metal salt Technical Field The invention belongs to the fields of nonaqueous electrolyte materials, power batteries and electrochemical energy storage, and relates to a preparation method of negative charge highly delocalized sulfimide alkali metal salt. Background The electrolyte conductive salt can provide carriers for the electrolyte body on the one hand and can participate in the formation and stabilization process of the electrode-electrolyte interface phase on the other hand. Therefore, the basic physical, chemical and electrochemical properties (e.g., chemical, electrochemical stability, electrode interface compatibility, etc.) of the conductive salt are closely related to the electrochemical performance of the secondary battery, and are one of the key materials for constructing a high specific energy secondary battery system. Existing commercial lithium ion batteries (Lithium-ion batteries, LIBs) generally employ nonaqueous liquid electrolytes based on lithium hexafluorophosphate (LiPF 6) as the primary conductive salt as the ion conductor, mainly due to the unique advantages of such electrolytes (1) higher ionic conductivity (about 10 -2S cm-1 at room temperature), (2) better resistance to corrosion by aluminum foil, and (3) a wider electrochemical window (> 4.5v vs. Li/Li +) [ see: K.Xu, chemical Reviews,2014,114,11503 ]. However, liPF 6 has poor chemical stability, and the electrolyte is easily decomposed under the action of proton impurities (such as water and hydrogen fluoride) to generate harmful substances such as phosphorus pentafluoride (PF 5), phosphorus oxytrifluoride (POF 3), hydrogen Fluoride (HF) and the like, so that the coulomb efficiency and the cycle stability of the battery are greatly reduced [ see, l.zheng, electrochimica Acta,2016,196,169-188 ]. In order to overcome the challenges, researchers in academia and industry continue to deeply plough the molecular structure design of the anions of the conductive salt, so as to overcome the defects of the traditional hexafluorophosphate radical system and meet the application requirements of the next-generation high-specific-energy battery. Wherein, the sulfimide anion [ -SO 2–N(-)–SO2 - ] has the characteristics of high delocalization of negative charge, high conformational freedom degree, strong structural designability and the like. The non-aqueous electrolyte based on alkali metal salts of sulfonimide anions has been shown to exhibit the advantages of excellent chemical stability (e.g., less hydrolysis, good tolerance to protonic impurities, etc.), higher thermal decomposition temperature (> 300 ℃), higher ionic conductivity, and wide electrochemical window, etc., and is considered to be an extremely promising class of alkali metal salts [ see: Q.Ma, chemElectroChem,2021,8 (10): 1807-1816 ]. For example, a nonaqueous liquid electrolyte using an asymmetric (perfluoroalkylsulfonyl) (polyfluoroalkoxysulfonyl) lithium imide as a conductive salt exhibits excellent properties such as high thermal stability, high oxidation-reduction resistance, and no corrosion of aluminum foil. In particular, batteries based on asymmetric (perfluoroalkylsulfonyl) (polyfluoroalkoxysulfonyl) lithium imides exhibit more excellent high temperature cycling stability and shelf storage performance than battery devices containing LiPF 6 conductive salts [ see: chinese patent CN103515650a ]. The perfluoroalkyl sulfonamide group (R 1SO2 N=) is adopted to replace oxygen atoms (O=) on sulfonyl, a novel negative-charge highly-delocalized sulfimide alkali metal salt is constructed, and a nonaqueous electrolyte material system with more excellent performance can be obtained, so that the performance of the secondary battery is improved. For example, replacing one oxygen atom (o=) in the bis (trifluoromethylsulfonyl) imide anion structure with a trifluoromethylsulfonyl imide group (CF 3SO2 n=) can effectively increase the degree of delocalization of the negative anionic charge, thereby improving the ionic conductivity of the non-aqueous electrolyte based on the sulfonimide anions [ see: H.Zhang, chemElectroChem,2021,8:1322-1328 ]. Furthermore, on the basis of the negative charge highly delocalized sulfimide structure, a substituent group containing unsaturated double bonds is introduced, so that a special anionic immobilized polyanion conductive salt can be prepared. The method is mainly characterized by (1) large molecular weight and large volume of anions, difficult migration and (2) high migration number of cations, which is close to 1. The prepared electrolyte material has the advantages of high ionic conductivity at room temperature, high cation migration number, good mechanical property, wide electrochemical window and the like, can effectively improve the interface stability of an electrode-electrolyte phase, and improves the cycle performance and high and low temperature performance of a ba