Ionic liquid prepared through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt

A technology of ionic liquids and alkali metal salts, applied in the field of H[RfFSI], can solve the problems of fluorosulfonic anhydride's high toxicity, difficult product separation, harsh reaction conditions, etc.

Inactive Publication Date: 2010-06-23
HUAZHONG UNIV OF SCI & TECH
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Problems solved by technology

The second and third step reactions of this preparation method have the following obvious disadvantages: 1) use AsF 3 When preparing H[FSI] as a fluorinating agent, there is FSO in the reaction process 3 H (boiling point 165°C) is formed, and its boiling point is very close to that of product H[FSI] (boiling point 170°C) (J.K.Ruff et al, Inorg.Synth.1968, 11, 138); product H[FSI] and by-products POCl 3 Formation of azeotrope (H[FSI].POCl 3 , 1:1) (J.K.Ruff, Inorg.Chem.1967, 6, 2108), and the boiling point and FSO 3 The proximity of H makes the separation and purification of H[FSI] very difficult
due to FSO 2 The use of F gas makes the method reaction condition harsh, complex operation, and the productive rate of product is not high (D.H.Richard et al, US 5874616,1999); 3) by trifluoromethanesulfonyl trichlorophosphazene (CF 3 SO 2 N=PCl 3 ) compound with chlorosulfonic acid (ClSO 3 H) reaction or chlorosulfonyl trichlorophosphazene ((ClSO 2 N=PCl 3 )) and trifluoromethanesulfonic acid (CF 3 SO 3 H) reaction to obtain (trifluoromethylsulfonyl chlorosulfonyl) imide (HN(SO 2 Cl)(SO 2 CF 3 )), the method synthesizes HN(SO 2 Cl)(SO 2 CF 3 ) yield is higher, but HN(SO 2 Cl)(SO 2 CF 3 ) reacts with a fluorinating reagent to carry out fluorination, the same problems as product separation difficulties and low purity will be encountered when the aforementioned preparation of H[FSI] is encountered (K.Xu et al, Inorg.Chem.Commun.1999, 2, 26)
4) from trifluoromethanesulfonamide potassium salt (CF 3 SO 2 NHK) and fluorosulfonic anhydride (FSO 2 ) 2 O) Reaction preparation, but fluorosulfonic anhydride is highly toxic, therefore, it is not suitable for large-scale preparation (S.Maehama et al, JP 2005200359, 2005)
And by H[CF 3 The ionic liquid synthesized by FSI] is rarely reported (S.Maehama et al, JP 2005200359, 2005)

Method used

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  • Ionic liquid prepared through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt
  • Ionic liquid prepared through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt
  • Ionic liquid prepared through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1-9

[0060] Examples 1-9 relate to H[FSI] and H[R f FSI] Preparation of Alkali Metal Salts

Embodiment 1

[0061] Example 1: Preparation of potassium bis(fluorosulfonyl)imide (K[FSI])

[0062] The synthesis reaction scheme is as follows:

[0063] HOSO 2 NH 2 +SOCl 2 +HOSO 2 Cl→H[N(SO 2 Cl) 2 ]+SO 2 ↑+HCl↑

[0064]

[0065] Under the protection of nitrogen, add 480 grams (5mol) of sulfamic acid, 1780 grams (15mol) of thionyl chloride, and 580 grams (0.5mol) of chlorosulfonic acid into a 5000mL reaction flask in sequence, and stir and react at 130°C for 24 hours , Atmospheric pressure distillation removes excessive low-boiling point reactant, then carries out vacuum distillation, collects the cut of 112-114 ℃ / 2mmHg, obtains two (chlorosulfonyl)imides (HN(SO 2 Cl) 2 ) 880 g (4.1 mol) of colorless crystals, yield 82%.

[0066] Under magnetic stirring and nitrogen protection, 96 grams (0.45mol) of bis(chlorosulfonyl)imide and 54 grams (0.3mol) of anhydrous antimony trifluoride were placed in a 500mL three-necked flask, and stirred at room temperature After reacting for 12 ...

Embodiment 2

[0068] Embodiment 2: Preparation of bis(fluorosulfonyl)imide cesium (Cs[FSI])

[0069] The synthesis reaction scheme is as follows:

[0070]

[0071] Under magnetic stirring and nitrogen protection, 9.6 grams (0.045mol) of bis(chlorosulfonyl)imide (prepared according to the operation of Example 1), and 5.4 grams (0.03mol) of anhydrous antimony trifluoride were placed in 100mL In a three-necked flask, after stirring for 12 hours at room temperature, 40 mL of acetonitrile was added to the reaction flask. After most of the solids were dissolved, 8.9 g (0.03 mol) of anhydrous cesium carbonate was added in portions under stirring, and the reaction was continued for 12 hours after the addition was complete. Then, the pH value of the system was adjusted to neutral with 2M HCl. Filter under reduced pressure to remove solid insoluble matter, concentrate the filtrate to about 7-10 mL, add an equal volume of CH 2 Cl 2Perform recrystallization. After filtering, washing and drying,...

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Abstract

The invention provides an ionic liquid consisting of the anions of diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine and the cation of sulfonium salt, ammonium salt or phosphor salt, as well as method for preparing the ionic liquid through diimine (vikane) and (perfluoroalkglsulfonyl fluorosulfonyl group) imine alkali salt. The ionic liquid can be used as an electrolyte material and applied on the fields like secondary lithium ion batteries, super capacitors, etc.

Description

technical field [0001] The present invention relates to ionic liquids, in particular to two (fluorosulfonyl) imides (H[N(SO 2 F) 2 ], referred to as H[FSI]) and (perfluoroalkylsulfonylfluorosulfonyl)imine (H[R f SO 2 NSO 2 F]), referred to as H[R f FSI];R f =C m f 2m+1 , m=1-8) anions and sulfonium salts, ammonium salts or phosphonium salt cations, and bis(fluorosulfonyl)imide (H[N(SO 2 f) 2 ]) and (perfluoroalkylsulfonylfluorosulfonyl)imine (H[R f SO 2 NSO 2 F], R f =C m f 2m+1 , m=1-8) alkali metal salt (M[N(SO 2 F) 2 ], M[R f SO 2 NSO 2 F)]; M=Li, Na, K, Rb, Cs) The method for preparing the ionic liquid also relates to the application of the ionic liquid as an electrolyte material in secondary lithium (ion) batteries, supercapacitors and other fields. Background technique [0002] Bis(fluorosulfonyl)imide (H[N(SO 2 F) 2 ], hereinafter referred to as H[FSI]) and (perfluoroalkylsulfonylfluorosulfonyl)imine (H[R f SO 2 NSO 2 F)], R f =C m f 2m+1 ,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C311/02C07C391/00C07C211/62C07C217/06C07D295/04C07D233/56C07F9/54H01G9/035H01M10/40
CPCY02E60/13
Inventor 周志彬韩洪波聂进刘凯郭鹏周宜轩
Owner HUAZHONG UNIV OF SCI & TECH
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