Granules or powder of disulfonylamide salt and method for producing same

Abstract

Granules or powders consisting of a compound of formula [I], in which a modal diameter is 80 m or less, a median diameter is 45 m or less, and/or, a ratio of (modal diameter)/(median diameter) is 1.7 or less, are preferably used for an electrolyte or the like. ##STR00001## In formula [I], R.sup.1 and R.sup.2 each independently represents a fluoroalkyl group having 1 to 6 carbon atoms, or a fluorine atom, and Y.sup.+ represents an alkali metal cation or an ammonium cation.

Claims

1. Granules or powders consisting of a compound of formula [I], wherein a modal diameter thereof is 5 m to 80 m: ##STR00004## in the formula [I], R.sup.1 and R.sup.2 each independently represents a fluoroalkyl group having 1 to 6 carbon atoms, or a fluorine atom, and Y.sup.+ represents an alkali metal cation, and wherein a concentration of a residual solvent is 800 ppm or less.

2. The granules or the powders according to claim 1, wherein R.sup.1 and R.sup.2 represent fluorine atoms.

3. The granules or the powders according to claim 1, wherein a median diameter is 5 m to 45 m and a ratio of (modal diameter) / (median diameter) is 1.7 or less.

4. The granules or the powders according to claim 3, wherein the modal diameter is 5 m to 39.619 m.

5. The granules or the powders according to claim 3, wherein the median diameter is 5 m to 39.658 m.

6. The granules or the powders according to claim 3, wherein the ratio of (modal diameter) / (median diameter) is 0.76 to 1.15.

7. Granules or powders consisting of a compound of formula [I], wherein a median diameter thereof is 45 m or less: ##STR00005## in the formula [I], R.sup.1 and R.sup.2 each independently represents a fluoroalkyl group having 1 to 6 carbon atoms, or a fluorine atom, and Y.sup.+ represents an alkali metal cation, wherein a concentration of a residual solvent is 800 ppm or less.

8. The granules or the powders according to claim 7, wherein the median diameter is 5 m to 45 m.

9. The granules or the powders according to claim 7, wherein R.sup.1 and R.sup.2 represent fluorine atoms.

10. Granules or powders consisting of a compound of formula [I], wherein a ratio of (modal diameter)/(median diameter) is 1.7 or less: ##STR00006## in the formula [I], R.sup.1 and R.sup.2 each independently represents a fluoroalkyl group having 1 to 6 carbon atoms, or a fluorine atom, and Y.sup.+ represents an alkali metal cation, and wherein a concentration of a residual solvent is 800 ppm or less.

11. The granules or the powders according to claim 10, wherein R.sup.1 and R.sup.2 represent fluorine atoms.

12. A method for producing granules or powders of claim 1, comprising adding an ester-based solvent solution comprising a compound of formula [I] to a halogenated hydrocarbon-based solvent: ##STR00007## in the formula [I], R.sup.1 and R.sup.2 each independently represents a fluoroalkyl group having 1 to 6 carbon atoms, or a fluorine atom, and Y.sup.+ represents an alkali metal cation; and allowing the granules of powders consisting of the compound of formula [I] to crystalize from the ester-based solvent and halogenated hydrocarbon-based solvent, wherein the modal diameter thereof is 5 m to 80 m.

13. The method according to claim 12, wherein a concentration of the compound of the formula [I] in the ester-based solvent solution is 20% by mass to 90% by mass.

Description

EXAMPLES

(1) The present invention is described below in further detail using a series of examples. The present invention is in no way limited by these examples, and can, of course, be practiced with modification as appropriate within a range that can be adaptable to the purposes of the present invention, and those are all encompassed in the technical scope of the present invention.

Synthesis Example 1

(2) Synthesis of di(chlorosulfonyl)amide

(3) 123.9 parts by mass of chlorosulfonic acid and 98.1 parts by mass of chlorosulfonyl isocyanate were put in a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser. While stirring the mixture, the temperature thereof was raised to 130 C. over a period of 2.5 hours, then the mixture was reacted for 9 hours at 130 C. Then, the resultant was distilled under reduced pressure to collect a fraction between 98.5 C. and 101 C. at 4.2 torr. 77.9 parts by mass of di(chlorosulfonyl)amide was obtained as a colorless transparent liquid.

Synthesis Example 2

(4) Synthesis of di(fluorosulfonyl) amide ammonium salt

(5) 1.07 parts by mass of di (chlorosulfonyl) amide obtained in Synthesis Example 1 was put in a fluorine resin reaction vessel. 7.9 parts by mass of acetonitrile and 0.89 parts by mass of ammonium fluoride were added thereto, and then reacted with refluxing the mixture for 4 hours at 80 C. to 84 C. Then, the resultant was cooled to room temperature, and the insoluble materials were filtered off, and then the resultant was washed with 7.9 parts by mass of acetonitrile. The solvent was then removed under reduced pressure to obtain 0.95 parts by mass of di (fluorosulfonyl) amide ammonium salt.

Example 1

(6) 33.4 parts by mass of di(fluorosulfonyl) amide ammonium salt, 69.5 parts by mass butyl acetate, and 102.5 parts by mass of 20% aqueous solution of potassium hydroxide were put in a reaction vessel, and then stirred for 1 hour at 40 C. under a reduced pressure at 100 torr. The reaction mixture was cooled to 25 C. Then, the reaction mixture was separated to obtain an aqueous phase, and then the aqueous phase was extracted twice with 81.1 parts by mass of butyl acetate. The resultant organic phases obtained in the extraction steps were mixed together, and then washed twice with 4.6 parts by mass of water. The solvent in the obtained organic phase was removed under reduced pressure to obtain 91.2 parts by mass of 39.1% by mass of di (fluorosulfonyl) amide potassium salt/butyl acetate solution. The yield was 97%.

(7) 91.2 parts by mass of 39.1% by mass of di (fluorosulfonyl) amide potassium salt/butyl acetate solution was added dropwise into 244.1 parts by mass of dichloromethane over a period of 52 minutes at 16 to 24 C. The resultant was cooled to 10 C. over a period of 1 hour. Then, the resultant was stirred at 7 to 10 C. for 42 minutes. The obtained slurry liquid was filtered and washed with 74.0 parts by mass of dichloromethane. The obtained solid was vacuum dried at 6 torr for 13.4 hours at 60 C. to yield 35.1 parts by mass of granules. The yield was 98% with respect to the charged amount of di(fluorosulfonyl)amide potassium salt. The granules had a median diameter of 34.563 m and a modal diameter of 26.121 m, and the concentration of the residual solvent therein was 370 ppm (dichloromethane 210 ppm, butyl acetate 160 ppm).

Example 2

(8) 71.7 parts by mass of 38.0% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution was obtained in the same manner as that of Example 1.

(9) 71.7 parts by mass of 38.0% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution was added dropwise into 167.6 parts by mass of dichloromethane over a period of 30 minutes at 19 to 20 C. The resultant was cooled to 10 C. over a period of 1 hour. Then, the resultant was stirred at 10 C. for 30 minutes. The obtained slurry liquid was filtered and washed with 50.3 parts by mass of dichloromethane. The obtained solid was vacuum dried at 2 torr for 1 hour at 40 C., and then vacuum dried at 0.5 torr for 2 hours at 60 C., to obtain 25.8 parts by mass of granules. The yield was 98% with respect to the charged amount of di(fluorosulfonyl)amide potassium salt. The granules had a median diameter of 35.313 m, and a modal diameter of 39.619 m, and the concentration of the residual solvent therein was 640 ppm (dichloromethane 550 ppm, butyl acetate 90 ppm).

Example 3

(10) 73.2 parts by mass of 36.5% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution was obtained in the same manner as that of Example 1.

(11) 73.2 parts by mass of 36.5% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution was added dropwise into 162.4 parts by mass of dichloromethane over a period of 29 minutes at 24 to 32 C. The resultant was cooled to 12 C. over a period of 2.1 hours. The obtained slurry liquid was filtered and washed with 48.8 parts by mass of dichloromethane. The obtained solid was vacuum dried at 8 to 10 torr for 18.1 hours at 60 C. to obtain 25.3 parts by mass of granules. The yield was 95% with respect to the charged amount of di(fluorosulfonyl)amide potassium salt. The granules had a median diameter of 39.658 m, and a modal diameter of 39.619 m, and the concentration of the residual solvent therein was 790 ppm (dichloromethane 430 ppm, butyl acetate 360 ppm).

Example 4

(12) 82.0 parts by mass of 37.3% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution was obtained in the same manner as that of Example 1.

(13) 82.0 parts by mass of 37.3% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution was added dropwise into 188.1 parts by mass of dichloromethane over a period of 30 minutes at 17 to 19 C. The resultant was cooled to 10 C. over a period of 32 minutes. Then, the resultant was stirred at 5 to 10 C. for 1.2 hours. The obtained slurry liquid was filtered and washed with 56.1 parts by mass of dichloromethane. The obtained solid was vacuum dried at 11 torr for 18.1 hours at 60 C. to obtain 15.5 parts by mass of granules. The yield was 98% with respect to the charged amount of di(fluorosulfonyl)amide potassium salt. The granules had a median diameter of 34.420 m, and a modal diameter of 39.619 m, and the concentration of the residual solvent therein was 1160 ppm (dichloromethane 800 ppm, butyl acetate 360 ppm).

Comparative Example 1

(14) 81.5 parts by mass of 38.8% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution was obtained in the same manner as that of Example 1.

(15) 194.2 parts by mass of dichloromethane was added dropwise into 81.5 parts by mass of 38.8% by mass of di(fluorosulfonyl)amide potassium salt/butyl acetate solution over a period of 39 minutes at 4 to 5 C. After the completion of the addition dropwise, the resultant was stirred at 4 to 5 C. for 1.4 hours. The obtained slurry liquid was filtered and washed with 57.9 parts by mass of dichloromethane. The obtained solid was vacuum dried at 5 torr for 12.3 hours at 60 C., vacuum dried at 4 torr for 20.5 hours at 60 C., and then vacuum dried at 6 torr for 18.9 hours at 60 C., to obtain 30.9 parts by mass of granules. The yield was 98% with respect to the charged amount of di(fluorosulfonyl)imide potassium salt. The granules had a median diameter of 51.796 m, and a modal diameter of 91.146 m, and the concentration of the residual solvent therein was 5100 ppm (dichloromethane 2300 ppm, butyl acetate 2800 ppm). The concentration of the residual solvent in the granules having a median diameter larger than 45 m, a modal diameter larger than 80 m, and a modal diameter/median diameter ratio larger than 1.7, did not decrease even after a long time drying.

(16) The above results shows that the concentration of the residual solvent is low in granules or powders in which the median diameter is adjusted to 45 m or less, the modal diameter is adjusted to 80 m or less, and/or, the ratio of modal diameter/median diameter is adjusted to 1.7 or less, in accordance with the present invention, and therefore the granules or powders are useful as an electrolyte for an electrolytic solution available in a secondary battery, a solar cell, or the like.

INDUSTRIAL APPLICABILITY

(17) Granules or powders according to the present invention can be quickly and uniformly dissolved in a solvent, and contribute to increase in efficiency of manufacturing an electrolytic solution available in a secondary cell, a solar cell, or the like. In addition, in the granules or powder according to the present invention, the content of impurities such as solvents, or metal ions, is low, and therefore, it is difficult to cause deterioration of cell characteristics.