CA2248376A1 - Process for the preparation of cyclic perfluoroalkanebis(sulfonyl)imides and such novel four-membered imides - Google Patents
Process for the preparation of cyclic perfluoroalkanebis(sulfonyl)imides and such novel four-membered imides Download PDFInfo
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- CA2248376A1 CA2248376A1 CA002248376A CA2248376A CA2248376A1 CA 2248376 A1 CA2248376 A1 CA 2248376A1 CA 002248376 A CA002248376 A CA 002248376A CA 2248376 A CA2248376 A CA 2248376A CA 2248376 A1 CA2248376 A1 CA 2248376A1
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- Prior art keywords
- sulfonyl
- imide
- lithium
- cyclo
- difluoromethanebis
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- 150000003949 imides Chemical class 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 17
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 5
- -1 imide ammonium salt Chemical class 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- JUXVYADNSPUZHF-UHFFFAOYSA-N difluoromethanedisulfonyl fluoride Chemical compound FS(=O)(=O)C(F)(F)S(F)(=O)=O JUXVYADNSPUZHF-UHFFFAOYSA-N 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/15—Six-membered rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Abstract
The invention relates to a process for the preparation of cyclic perfluoroalkanebis(sulfonyl)imides and salts thereof. The new compound lithium cyclodifluoromethanebis(sulfonyl)imide is outstandingly suitable as a conductive salt in non-aqueous electrolytes for lithium secondary batteries.
Description
W O 97/31909 PCT~EP97/00819 PROCESS FOR THE PREPARATION OF CYCLIC PERFLUOROALKANEBIS(SULFONYL)IMIDES AND
SUCH NOVEL FOUR-MEMBERED IMIDES
The invention relates to a process for the preparation of cyclic perfluoroalkanebis(sulfonyl)-imides and salts thereof.
Cyclic perfluoroalkanebis(sulfonyl)imides, and salts of these compounds, which contain at least two ring carbon atoms are known from EP 0 057 327 B1.
Compounds of this type can be obtained from corresponding open-chain precursors by a cycli,_ation reaction. According to the patent specification mentioned, the compounds are prepared by passing gaseous ammonia through a solution of a corresponding perfluoroalkane-bis-sulfonyl fluoride. Ring compounds which are initially obtained in the form of the ammonium salts are formed by this procedure. The imides or imide salts with other cations can be obtained by an exchange reaction.
It is known from WO 88/03331 that cyclic perfiuoroalkanebis(sulfonyl)imide salts prepared in this way, such as, in particular, the corresponding lithium salts, can be employed as conductive salts in non-aqueous electrolytes for lithium secondary batteries.
It can be seen from EP 0 057 327 B1 that the preparation process described therein gives only product yields which are not very satisfactory. Our studies confirm this, and furthermore show that the target products are obtained in a form contaminated with undesirable by-products and other impurities, from which they can be separated off only with difficulty and with further losses in yield. However, a high and reproducible purity of these compounds is of essential importance for use as a constituent of battery electrolytes.
It has now been found that cyclic perfluoroalkanebis(sulfonyl)imides and salts thereof can be obtained in a virtually quantitative yield and in a form which is largely free from by-products and W O 97/31909 - 2 - PCT~EP97/00819 impurities if a solution of the corresponding perfluoroalkane-bis-sulfonyl fluoride is metered slowly and with intensive thorough mixing into liquid ammonia.
It has furthermore been found that the compound cyclo-difluoromethanebis(sulfonyl)imide, which is new per se, and salts thereof can be obtained by the process according to the invention.
The invention thus relates to a process for the preparation of cyclic perfluoroalkanebis(sulfonyl)-imides and salts thereof by a cyclization reaction ofcorresponding perfluoroalkane-bis-sulfonyl fluorides in which a solution of the perfluoroalkane-bis-sulfonyl fluoride is metered slowly and with intensive thorough mixing into liquid ammonia.
The invention furthermore relates to the new ammonium and lithium salts of cyclo-difluoromethanebis-(sulfonyl)imide.
The invention moreover relates to the use of lithium cyclo-difluoromethanebis(sulfonyl)imide as a conductive salt in non-aqueous electrolytes for lithium secondary batteries.
The invention finally relates to non-aqueous electrolytes for lithium secondary batteries which comprise the compound lithium cyclo-difluoromethanebis-(sulfonyl)imide, and lithium secondary batteries whichcomprise such electrolytes.
The process according to the invention starts from the same non-cyclic starting compounds and is based in principle on the same cyclization reaction as the known processes. However, an essential difference is that in this case the starting compound is cyclized in and at the temperature of liquid ammonia, the reaction partner ammonia always being present in excess in the course of the reaction because of the reaction conditions chosen. The formation of by-products and impurities is presumably largely suppressed by this excess ammonia and the low reaction temperature.
Liquid ammonia is produced in a manner known per se by condensation of ammonia gas with appropriate cooling. The temperature of the liquid ammonia is -70~C
or even lower. Cooling which is suitable for the laboratory to pilot plant scale can be effected with the aid of dry ice (solid carbon dioxide), methanol/dry ice refrigerating mixtures or with liquid nitrogen. The liquefaction is carried out by condensing the ammonia gas into the cooled reaction vessel.
The perfluoroalkanebis(sulfonyl)imide is employed in the form of a solution in a suitable organic solvent. Tetrahydrofuran (THF) has proved favourable as the solvent. It is expedient also to take up the liquid ammonia condensate in THF. For carrying out the cyclization reaction, the solution of the starting substance is metered slowly and with intensive thorough mixing into the liquid ammonia or its THF
solution. The addition can be carried out in small portions, for example by dropwise addition, and the thorough mixing can be carried out by stirring the reaction mixture. It is to be ensured here that the reaction mixture is kept at the temperature of the liquid ammonia and corresponding heat of reaction is removed by cooling. When the reaction has ended and the excess ammonia has been evaporated off, the target product can be obtained in the form of the corresponding ammonium salt by extracting the residue with THF and removing the solvent. The reaction yield is high to virtually quantitative. As a rule, further purification operations are not necessary.
The ammonium cyclo-perfluoroalkanebis-(sulfonyl)imides thus obtained can be converted intothe corresponding imides or into other metal salts by a simple exchange reaction. Conversion into corresponding lithium salts by reaction with lithium hydroxide is of particular interest. This reaction also proceeds virtually quantitatively without the formation of by-products and impurities.
For this reaction, for example, the ammonium compound is boiled with lithium hydroxide monohydrate in THF until no further ammonia forms.
W O 97/31909 - 4 - PCT~P97/00819 The yield is also virtually quantitative in this process step.
It is surprising that the homologous 4-membered ring compounds, which have not hitherto been described, can be obtained by the process according to the invention. These are the compounds cyclo-difluoro-methanebis(sulfonyl)imide and the corresponding ammonium and lithium salts.
Against generally accepted expectations, it has furthermore been found that the abovementioned 4-membered ring compounds are exceptionally stable.
Thus, no decomposition occurs during dry storage at a temperature of 100~C. Only from temperatures above 230~C are slight yellow discolorations of the otherwise colourless material found after several hours. Also after storage in solution, for example in organic solvents, such as THF or acetonitrile, no changes in colour can be found and no decomposition products are to be detected even after weeks.
For this reason alone, the new compound lithium cyclo-difluoromethanebis(sulfonyl)imide according to the invention is outstandingly suitable as a conductive salt in non-aqueous electrolytes for lithium secondary batteries.
In addition to organolithium salts, as the abovementioned compound is, such electrolytes comprise one or more non-aqueous organic solvents and, if appropriate, further additives. Further details on such electrolytes and the build-up and mode of functioning of lithium secondary batteries are known to the relevant expert. The compound according to the invention can be employed in complete analogy to the lithium compounds known for this use. The compound according to the invention likewise shows an exceptional stability here. The corresponding battery cells show outstanding properties in respect of capacity and constant voltage and unrestricted - functional capacity over an above-average high number of charging-discharging cycles.
~am~le 1 ~m~onium cyclo-perfluoroalkane-l,n-bis(sulfonyl)imides 55 ml of anhydrous ammonia are condensed through a gas inlet tube into a two-necked flask of 250 ml capacity which is cooled with dry ice and provided with an intensive cooler (temperature -70~C).
Thereafter, the inlet tube is replaced by a dropping funnel and 55 ml of dry THF are added dropwise.
A solution of 200 mmol of the particular perfluoroalkane-l,n-bis(sulfonyl fluoride) (n = 1-3) in 100 ml of THF are then slowly added dropwise (120 minutes) to the THF-ammonia solution, while stirring. During the dropwise addition, the reaction flask is cooled further with dry ice.
During the exothermic reaction, the ammonium fluoride which forms and also some of the ammonium imide formed precipitate out. When the reaction has ended, the ammonia which remains is allowed to evaporate by warming the suspension to room temperature. The precipitate is extracted with lO0 ml of THF over a frit.
The combined THF solutions are freed from the solvent by distillation and the colourless solid which remains is dried in vacuo at 40~C.
Table 1: ~mmonium cyclo-perfluoroalkane-l,n-bis-(sulfonyl)imides (n=1-3) nmeduct Yield Mproduct Empirical [g] [g] [g mol~1~ formula l 43.2229.42 g or 70% 210.17 CH4F2N2O4s2 2 53.2344.75 g or 86% 260.18 C2H4F4N2O4s2 3 63.2350.25 g or 81% 310.19 C3H4F6N2O4s2 W O 97131909 - 6 - PCT~EP97/00819 ~Y~le 2:
Lithium cyclo-perf}uoroalkane-l,n-bis(sulfonyl)imides 4.6 g (110 mmol) of lithium hydroxide monohydrate are added to a solution of 100 mmol of the corresponding ammonium cyclo-perfluoroalkane-l,n-bis(sulfonyl)imide in 60 ml of THF, while stirring. The suspension is boiled until no further evolution of ammonia can be detected (about 120 mins). After filtration of the reaction solution and removal of the solvent, the solid which remains is taken up in water and boiled with active charcoal (about 180 mins).
Thereafter, the suspension is filtered, the water is stripped off and the colourless solid which remains is dried under a high vacuum. This solid is then dissolved again in 50 ml of anhydrous THF, the solution is filtered and the solvent is removed again.
In order to free the lithium imides from still-adhering THF residues, these are suspended three timesin 50-60 ml of n-pentane, the solvent being removed again each time.
The lithium cyclo-perfluoroalkane-l,n-bis(sulfonyl)imides are then dried on a water bath under a high vacuum for 8 hours. Colourless, crystalline salts are obtained.
Table 2: Lithium cyclo-perfluoroal~ane-l,n-bis-(~ulfonyl)imide (n=1-3) nmeduct Yield MprOdu~t Empirical [g] [g] [g mol~l] formula 1 21.0219.31 g or 97~ 199.07 CF2LiNO9s2 2 26.0224.16 g or 97~ 249.08 C2F4LiNO4s2 3 31.0228.71 g or 96~ 299.09 C3F6LiNO4s2 W O 97t31909 - 7 _ PCT~EP97/00819 Lithium cyclo-difluoromethane-1,1-bis(sulfonyl)imide:
Lithium content: found: 3.49% calculated: 3.49~
C-NMR (CD3CN, 75.4 MHz, total): ~ = 133.94 (t, JCF
366.9 Hz) F-NMR(CD3CN, C6F6 external), 75.4 MHz): ~ = -86.95 (s) Lithium cyclo-tetrafluoroethane-1,2-bis(sulfonyl)-imide:
Lithium content: found: 2.80% calculated: 2.79~
3C-NMR(CD3CN, 125.76 MHz, 30% by weight): ~ = 115.58 (tt, JCF = 306.6 HZ ), JCF = 22.6 Hz ) lgF-NMR (CD3CN, C6F6 external), 75.4 MHz, 30~ by weight):
~= - 113.72 ( s) Lithium cyclo-hexafluoropropane-1,3-bi~(sulfonyl)-imide:
Lithium content: found: 2.31% calculated: 2.31~
C-NMR (CD3CN, 125.76 MHz, 30% by weight): ~ = 110. 72 (tqi, JCF = 273. ~ Hz), JCF = 25 - 5 HZ), 113. 96 (tt, JCF
= 298.1 Hz), JCF = 25.3 Hz) l9F-NMR (CD3CN, C6F6 external), 75.4 MHz, 30% by weight):
2 5 ~ = - 125.21 ( qi, JFF = 8.6 Hz ), - 118.77 ( t, JFF = 8.5 Hz ) . .
SUCH NOVEL FOUR-MEMBERED IMIDES
The invention relates to a process for the preparation of cyclic perfluoroalkanebis(sulfonyl)-imides and salts thereof.
Cyclic perfluoroalkanebis(sulfonyl)imides, and salts of these compounds, which contain at least two ring carbon atoms are known from EP 0 057 327 B1.
Compounds of this type can be obtained from corresponding open-chain precursors by a cycli,_ation reaction. According to the patent specification mentioned, the compounds are prepared by passing gaseous ammonia through a solution of a corresponding perfluoroalkane-bis-sulfonyl fluoride. Ring compounds which are initially obtained in the form of the ammonium salts are formed by this procedure. The imides or imide salts with other cations can be obtained by an exchange reaction.
It is known from WO 88/03331 that cyclic perfiuoroalkanebis(sulfonyl)imide salts prepared in this way, such as, in particular, the corresponding lithium salts, can be employed as conductive salts in non-aqueous electrolytes for lithium secondary batteries.
It can be seen from EP 0 057 327 B1 that the preparation process described therein gives only product yields which are not very satisfactory. Our studies confirm this, and furthermore show that the target products are obtained in a form contaminated with undesirable by-products and other impurities, from which they can be separated off only with difficulty and with further losses in yield. However, a high and reproducible purity of these compounds is of essential importance for use as a constituent of battery electrolytes.
It has now been found that cyclic perfluoroalkanebis(sulfonyl)imides and salts thereof can be obtained in a virtually quantitative yield and in a form which is largely free from by-products and W O 97/31909 - 2 - PCT~EP97/00819 impurities if a solution of the corresponding perfluoroalkane-bis-sulfonyl fluoride is metered slowly and with intensive thorough mixing into liquid ammonia.
It has furthermore been found that the compound cyclo-difluoromethanebis(sulfonyl)imide, which is new per se, and salts thereof can be obtained by the process according to the invention.
The invention thus relates to a process for the preparation of cyclic perfluoroalkanebis(sulfonyl)-imides and salts thereof by a cyclization reaction ofcorresponding perfluoroalkane-bis-sulfonyl fluorides in which a solution of the perfluoroalkane-bis-sulfonyl fluoride is metered slowly and with intensive thorough mixing into liquid ammonia.
The invention furthermore relates to the new ammonium and lithium salts of cyclo-difluoromethanebis-(sulfonyl)imide.
The invention moreover relates to the use of lithium cyclo-difluoromethanebis(sulfonyl)imide as a conductive salt in non-aqueous electrolytes for lithium secondary batteries.
The invention finally relates to non-aqueous electrolytes for lithium secondary batteries which comprise the compound lithium cyclo-difluoromethanebis-(sulfonyl)imide, and lithium secondary batteries whichcomprise such electrolytes.
The process according to the invention starts from the same non-cyclic starting compounds and is based in principle on the same cyclization reaction as the known processes. However, an essential difference is that in this case the starting compound is cyclized in and at the temperature of liquid ammonia, the reaction partner ammonia always being present in excess in the course of the reaction because of the reaction conditions chosen. The formation of by-products and impurities is presumably largely suppressed by this excess ammonia and the low reaction temperature.
Liquid ammonia is produced in a manner known per se by condensation of ammonia gas with appropriate cooling. The temperature of the liquid ammonia is -70~C
or even lower. Cooling which is suitable for the laboratory to pilot plant scale can be effected with the aid of dry ice (solid carbon dioxide), methanol/dry ice refrigerating mixtures or with liquid nitrogen. The liquefaction is carried out by condensing the ammonia gas into the cooled reaction vessel.
The perfluoroalkanebis(sulfonyl)imide is employed in the form of a solution in a suitable organic solvent. Tetrahydrofuran (THF) has proved favourable as the solvent. It is expedient also to take up the liquid ammonia condensate in THF. For carrying out the cyclization reaction, the solution of the starting substance is metered slowly and with intensive thorough mixing into the liquid ammonia or its THF
solution. The addition can be carried out in small portions, for example by dropwise addition, and the thorough mixing can be carried out by stirring the reaction mixture. It is to be ensured here that the reaction mixture is kept at the temperature of the liquid ammonia and corresponding heat of reaction is removed by cooling. When the reaction has ended and the excess ammonia has been evaporated off, the target product can be obtained in the form of the corresponding ammonium salt by extracting the residue with THF and removing the solvent. The reaction yield is high to virtually quantitative. As a rule, further purification operations are not necessary.
The ammonium cyclo-perfluoroalkanebis-(sulfonyl)imides thus obtained can be converted intothe corresponding imides or into other metal salts by a simple exchange reaction. Conversion into corresponding lithium salts by reaction with lithium hydroxide is of particular interest. This reaction also proceeds virtually quantitatively without the formation of by-products and impurities.
For this reaction, for example, the ammonium compound is boiled with lithium hydroxide monohydrate in THF until no further ammonia forms.
W O 97/31909 - 4 - PCT~P97/00819 The yield is also virtually quantitative in this process step.
It is surprising that the homologous 4-membered ring compounds, which have not hitherto been described, can be obtained by the process according to the invention. These are the compounds cyclo-difluoro-methanebis(sulfonyl)imide and the corresponding ammonium and lithium salts.
Against generally accepted expectations, it has furthermore been found that the abovementioned 4-membered ring compounds are exceptionally stable.
Thus, no decomposition occurs during dry storage at a temperature of 100~C. Only from temperatures above 230~C are slight yellow discolorations of the otherwise colourless material found after several hours. Also after storage in solution, for example in organic solvents, such as THF or acetonitrile, no changes in colour can be found and no decomposition products are to be detected even after weeks.
For this reason alone, the new compound lithium cyclo-difluoromethanebis(sulfonyl)imide according to the invention is outstandingly suitable as a conductive salt in non-aqueous electrolytes for lithium secondary batteries.
In addition to organolithium salts, as the abovementioned compound is, such electrolytes comprise one or more non-aqueous organic solvents and, if appropriate, further additives. Further details on such electrolytes and the build-up and mode of functioning of lithium secondary batteries are known to the relevant expert. The compound according to the invention can be employed in complete analogy to the lithium compounds known for this use. The compound according to the invention likewise shows an exceptional stability here. The corresponding battery cells show outstanding properties in respect of capacity and constant voltage and unrestricted - functional capacity over an above-average high number of charging-discharging cycles.
~am~le 1 ~m~onium cyclo-perfluoroalkane-l,n-bis(sulfonyl)imides 55 ml of anhydrous ammonia are condensed through a gas inlet tube into a two-necked flask of 250 ml capacity which is cooled with dry ice and provided with an intensive cooler (temperature -70~C).
Thereafter, the inlet tube is replaced by a dropping funnel and 55 ml of dry THF are added dropwise.
A solution of 200 mmol of the particular perfluoroalkane-l,n-bis(sulfonyl fluoride) (n = 1-3) in 100 ml of THF are then slowly added dropwise (120 minutes) to the THF-ammonia solution, while stirring. During the dropwise addition, the reaction flask is cooled further with dry ice.
During the exothermic reaction, the ammonium fluoride which forms and also some of the ammonium imide formed precipitate out. When the reaction has ended, the ammonia which remains is allowed to evaporate by warming the suspension to room temperature. The precipitate is extracted with lO0 ml of THF over a frit.
The combined THF solutions are freed from the solvent by distillation and the colourless solid which remains is dried in vacuo at 40~C.
Table 1: ~mmonium cyclo-perfluoroalkane-l,n-bis-(sulfonyl)imides (n=1-3) nmeduct Yield Mproduct Empirical [g] [g] [g mol~1~ formula l 43.2229.42 g or 70% 210.17 CH4F2N2O4s2 2 53.2344.75 g or 86% 260.18 C2H4F4N2O4s2 3 63.2350.25 g or 81% 310.19 C3H4F6N2O4s2 W O 97131909 - 6 - PCT~EP97/00819 ~Y~le 2:
Lithium cyclo-perf}uoroalkane-l,n-bis(sulfonyl)imides 4.6 g (110 mmol) of lithium hydroxide monohydrate are added to a solution of 100 mmol of the corresponding ammonium cyclo-perfluoroalkane-l,n-bis(sulfonyl)imide in 60 ml of THF, while stirring. The suspension is boiled until no further evolution of ammonia can be detected (about 120 mins). After filtration of the reaction solution and removal of the solvent, the solid which remains is taken up in water and boiled with active charcoal (about 180 mins).
Thereafter, the suspension is filtered, the water is stripped off and the colourless solid which remains is dried under a high vacuum. This solid is then dissolved again in 50 ml of anhydrous THF, the solution is filtered and the solvent is removed again.
In order to free the lithium imides from still-adhering THF residues, these are suspended three timesin 50-60 ml of n-pentane, the solvent being removed again each time.
The lithium cyclo-perfluoroalkane-l,n-bis(sulfonyl)imides are then dried on a water bath under a high vacuum for 8 hours. Colourless, crystalline salts are obtained.
Table 2: Lithium cyclo-perfluoroal~ane-l,n-bis-(~ulfonyl)imide (n=1-3) nmeduct Yield MprOdu~t Empirical [g] [g] [g mol~l] formula 1 21.0219.31 g or 97~ 199.07 CF2LiNO9s2 2 26.0224.16 g or 97~ 249.08 C2F4LiNO4s2 3 31.0228.71 g or 96~ 299.09 C3F6LiNO4s2 W O 97t31909 - 7 _ PCT~EP97/00819 Lithium cyclo-difluoromethane-1,1-bis(sulfonyl)imide:
Lithium content: found: 3.49% calculated: 3.49~
C-NMR (CD3CN, 75.4 MHz, total): ~ = 133.94 (t, JCF
366.9 Hz) F-NMR(CD3CN, C6F6 external), 75.4 MHz): ~ = -86.95 (s) Lithium cyclo-tetrafluoroethane-1,2-bis(sulfonyl)-imide:
Lithium content: found: 2.80% calculated: 2.79~
3C-NMR(CD3CN, 125.76 MHz, 30% by weight): ~ = 115.58 (tt, JCF = 306.6 HZ ), JCF = 22.6 Hz ) lgF-NMR (CD3CN, C6F6 external), 75.4 MHz, 30~ by weight):
~= - 113.72 ( s) Lithium cyclo-hexafluoropropane-1,3-bi~(sulfonyl)-imide:
Lithium content: found: 2.31% calculated: 2.31~
C-NMR (CD3CN, 125.76 MHz, 30% by weight): ~ = 110. 72 (tqi, JCF = 273. ~ Hz), JCF = 25 - 5 HZ), 113. 96 (tt, JCF
= 298.1 Hz), JCF = 25.3 Hz) l9F-NMR (CD3CN, C6F6 external), 75.4 MHz, 30% by weight):
2 5 ~ = - 125.21 ( qi, JFF = 8.6 Hz ), - 118.77 ( t, JFF = 8.5 Hz ) . .
Claims (11)
1. Process for the preparation of cyclic perfluoroalkanebis(sulfonyl)imides and salts thereof by a cyclization reaction of corresponding perfluoroalkane-bis-sulfonyl fluorides, characterized in that a solution of the perfluoroalkane-bis-sulfonyl fluoride is metered slowly and with intensive thorough mixing into liquid ammonia.
2. Process according to Claim 1, characterized in that the perfluoroalkane-bis-sulfonyl fluoride is dissolved in THF.
3. Process according to Claim 1 or 2, characterized in that the cyclic perfluoroalkanebis(sulfonyl)imide ammonium salt initially obtained is converted into the corresponding imide or into another metal salt by an exchange reaction.
4. Process according to Claim 3, characterized in that the cyclic perfluoroalkanebis(sulfonyl)imide ammonium salt is reacted with lithium hydroxide, the corresponding lithium salt being obtained.
5. Process according to Claim 1 or 2, characterized in that difluoromethanebis-sulfonyl fluoride is converted into ammonium cyclo-difluoromethanebis(sulfonyl)imide.
6. Process according to Claim 5, characterized in that the product is then reacted with lithium hydroxide to give lithium cyclo-difluoromethanebis-(sulfonyl)imide.
7. The compounds of the group cyclo-difluoromethanebis(sulfonyl)imide ammonium cyclo-difluoromethanebis(sulfonyl)imide and lithium cyclo-difluoromethanebis(sulfonyl)imide.
8 The compound lithium cyclo-difluoromethanebis-(sulfonyl)imide.
9. Use of the compound lithium cyclo-difluoromethanebis(sulfonyl)imide as a conductive salt in non-aqueous electrolytes for lithium secondary batteries.
10. Non-aqueous electrolytes for lithium secondary batteries comprising the compound lithium cyclo-difluoromethanebis(sulfonyl)imide.
11. Lithium secondary batteries comprising an electrolyte according to Claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19607832.6 | 1996-03-01 | ||
| DE19607832A DE19607832A1 (en) | 1996-03-01 | 1996-03-01 | Process for the preparation of cyclic perfluoroalkane bis (sulfonyl) imides and their salts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2248376A1 true CA2248376A1 (en) | 1997-09-04 |
Family
ID=7786881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002248376A Abandoned CA2248376A1 (en) | 1996-03-01 | 1997-02-20 | Process for the preparation of cyclic perfluoroalkanebis(sulfonyl)imides and such novel four-membered imides |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US6107493A (en) |
| EP (1) | EP0891342B1 (en) |
| JP (1) | JP2000506132A (en) |
| KR (1) | KR19990087426A (en) |
| CN (1) | CN1072656C (en) |
| AT (1) | ATE216991T1 (en) |
| CA (1) | CA2248376A1 (en) |
| CZ (1) | CZ267998A3 (en) |
| DE (2) | DE19607832A1 (en) |
| ES (1) | ES2176677T3 (en) |
| HU (1) | HUP9900989A2 (en) |
| ID (1) | ID16764A (en) |
| TW (1) | TW353816B (en) |
| WO (1) | WO1997031909A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2004001882A1 (en) * | 2002-06-19 | 2003-12-31 | Bridgestone Corporation | Supporting electrolyte for cell and method for production thereof, and cell |
| DE602004007245D1 (en) * | 2003-02-14 | 2007-08-09 | Chemson Polymer Additive Ag | USE OF SALTS OF SUPERACIC ACIDS AS A STABILIZER IN VINYL HALOGENIDE POLYMERS |
| CN101155777B (en) * | 2005-04-01 | 2012-04-04 | 旭硝子株式会社 | The production method of disulfonyl fluoride compound |
| DE102006011933B4 (en) * | 2006-03-15 | 2010-04-15 | Baerlocher Gmbh | Stabilizer compositions for halogen-containing polymers having improved initial color and improved color retention, polymer compositions containing them and shaped articles, and methods for stabilizing halogen-containing polymers |
| JP5158073B2 (en) * | 2007-03-12 | 2013-03-06 | 旭硝子株式会社 | Method for producing difluoromethane bis (sulfonyl fluoride) |
| JP2008230990A (en) * | 2007-03-19 | 2008-10-02 | Asahi Kasei Corp | Method for producing cyclic sulfonimide compound |
| CN101778835B (en) * | 2007-08-17 | 2013-03-20 | 旭硝子株式会社 | Process for producing refined ammonium salt of fluorine-containing disulfonylimide |
| JP2011044352A (en) * | 2009-08-21 | 2011-03-03 | Sony Corp | Electrolyte and battery |
| WO2012108284A1 (en) | 2011-02-10 | 2012-08-16 | 日本曹達株式会社 | Process for production of fluorosulfonylimide ammonium salt |
| SG192235A1 (en) * | 2011-03-03 | 2013-09-30 | Nippon Soda Co | Process for producing fluorine-containing sulfonylimide salt |
| US8604942B2 (en) | 2011-11-08 | 2013-12-10 | Honeywell International Inc. | System and method for displaying a velocity rate-of-change indicator |
| JP6050071B2 (en) * | 2012-09-20 | 2016-12-21 | 三菱マテリアル電子化成株式会社 | Adhesive composition |
| KR101955452B1 (en) | 2017-04-28 | 2019-03-11 | 주식회사 천보 | Manufacturing Method For bis-Fluoro Sulfonyl Imide Salt |
| CN107987035A (en) * | 2017-11-14 | 2018-05-04 | 石家庄圣泰化工有限公司 | The preparation method of high-performance lithium salts |
| KR20190059163A (en) | 2017-11-22 | 2019-05-30 | 주식회사 천보 | Manufacturing Method For bis-Fluoro Sulfonyl Imide Salt |
| KR102064904B1 (en) | 2018-01-08 | 2020-01-10 | 주식회사 천보 | Manufacturing Method For bis-Fluoro Sulfonyl Imide Salt |
| KR102064905B1 (en) | 2018-01-08 | 2020-01-10 | 주식회사 천보 | Manufacturing Method For bis-Fluoro Sulfonyl Imide Salt |
| CN109467539A (en) * | 2018-10-31 | 2019-03-15 | 蒋玉贵 | A kind of preparation method and purification process of the compound containing at least one cyclic ligand structure |
| CN113195551A (en) * | 2018-12-19 | 2021-07-30 | Ａｇｃ株式会社 | Polymer, method for producing polymer, and method for producing film |
| US11267707B2 (en) * | 2019-04-16 | 2022-03-08 | Honeywell International Inc | Purification of bis(fluorosulfonyl) imide |
| JP2023034119A (en) * | 2021-08-30 | 2023-03-13 | 旭化成株式会社 | Fluorine-containing cyclic sulfonyl imide salt |
| JP2023034097A (en) * | 2021-08-30 | 2023-03-13 | 旭化成株式会社 | Fluorine-containing cyclic sulfonyl imide salt |
| JP2023034103A (en) * | 2021-08-30 | 2023-03-13 | 旭化成株式会社 | Fluorine-containing cyclic sulfonyl imide salt |
| JP2023034110A (en) * | 2021-08-30 | 2023-03-13 | 旭化成株式会社 | Fluorine-containing cyclic sulfonyl imide salt |
| JP2023034088A (en) * | 2021-08-30 | 2023-03-13 | 旭化成株式会社 | Fluorine-containing cyclic sulfonyl imide salt |
| JP2023034081A (en) * | 2021-08-30 | 2023-03-13 | 旭化成株式会社 | Fluorine-containing cyclic sulfonyl imide salt |
| JP2023034118A (en) * | 2021-08-30 | 2023-03-13 | 旭化成株式会社 | Fluorine-containing cyclic sulfonyl imide salt |
| JP7754123B2 (en) * | 2023-03-31 | 2025-10-15 | トヨタ自動車株式会社 | Molecular crystal, electrochemical device, and method for manufacturing molecular crystal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4387222A (en) * | 1981-01-30 | 1983-06-07 | Minnesota Mining And Manufacturing Company | Cyclic perfluoroaliphaticdisulfonimides |
| US4429093A (en) * | 1981-01-30 | 1984-01-31 | Minnesota Mining And Manufacturing Co. | Cyclic perfluoroaliphaticdisulfonimides as polymerization catalysts |
| FR2606217B1 (en) * | 1986-10-30 | 1990-12-14 | Elf Aquitaine | NOVEL ION CONDUCTIVE MATERIAL CONSISTING OF A SALT SOLUTION IN A LIQUID ELECTROLYTE |
| US5652072A (en) * | 1995-09-21 | 1997-07-29 | Minnesota Mining And Manufacturing Company | Battery containing bis(perfluoroalkylsulfonyl)imide and cyclic perfluoroalkylene disulfonylimide salts |
-
1996
- 1996-03-01 DE DE19607832A patent/DE19607832A1/en not_active Withdrawn
-
1997
- 1997-02-20 AT AT97903342T patent/ATE216991T1/en not_active IP Right Cessation
- 1997-02-20 JP JP9530564A patent/JP2000506132A/en active Pending
- 1997-02-20 DE DE69712333T patent/DE69712333T2/en not_active Expired - Fee Related
- 1997-02-20 ES ES97903342T patent/ES2176677T3/en not_active Expired - Lifetime
- 1997-02-20 EP EP97903342A patent/EP0891342B1/en not_active Expired - Lifetime
- 1997-02-20 CN CN97192639A patent/CN1072656C/en not_active Expired - Fee Related
- 1997-02-20 CA CA002248376A patent/CA2248376A1/en not_active Abandoned
- 1997-02-20 US US09/125,949 patent/US6107493A/en not_active Expired - Fee Related
- 1997-02-20 CZ CZ982679A patent/CZ267998A3/en unknown
- 1997-02-20 KR KR1019980706846A patent/KR19990087426A/en not_active Ceased
- 1997-02-20 HU HU9900989A patent/HUP9900989A2/en unknown
- 1997-02-20 WO PCT/EP1997/000819 patent/WO1997031909A1/en not_active Ceased
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- 1997-03-06 TW TW86102737A patent/TW353816B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| DE69712333T2 (en) | 2002-11-14 |
| CN1212688A (en) | 1999-03-31 |
| ID16764A (en) | 1997-11-06 |
| JP2000506132A (en) | 2000-05-23 |
| ES2176677T3 (en) | 2002-12-01 |
| CN1072656C (en) | 2001-10-10 |
| US6107493A (en) | 2000-08-22 |
| DE19607832A1 (en) | 1997-09-04 |
| ATE216991T1 (en) | 2002-05-15 |
| WO1997031909A1 (en) | 1997-09-04 |
| HUP9900989A2 (en) | 1999-06-28 |
| DE69712333D1 (en) | 2002-06-06 |
| CZ267998A3 (en) | 1998-12-16 |
| EP0891342A1 (en) | 1999-01-20 |
| KR19990087426A (en) | 1999-12-27 |
| TW353816B (en) | 1999-03-01 |
| EP0891342B1 (en) | 2002-05-02 |
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