CA2527802A1 - Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent - Google Patents
Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent Download PDFInfo
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- -1 imides lithium salts Chemical class 0.000 title claims abstract description 32
- 229910003002 lithium salt Inorganic materials 0.000 title claims description 15
- 230000015572 biosynthetic process Effects 0.000 title abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 58
- 239000002253 acid Substances 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 150000003949 imides Chemical class 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 229910005143 FSO2 Inorganic materials 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims 3
- 229910020364 ClSO2 Inorganic materials 0.000 claims 2
- 239000007792 gaseous phase Substances 0.000 claims 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims 2
- 229910018926 (FSO2)2NLi Inorganic materials 0.000 abstract description 5
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 15
- 229910010941 LiFSI Inorganic materials 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910013131 LiN Inorganic materials 0.000 description 6
- 229910001290 LiPF6 Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000004293 19F NMR spectroscopy Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910006095 SO2F Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910017050 AsF3 Inorganic materials 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910019256 POF3 Inorganic materials 0.000 description 2
- 101100408805 Schizosaccharomyces pombe (strain 972 / ATCC 24843) pof3 gene Proteins 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- JCMGUODNZMETBM-UHFFFAOYSA-N arsenic trifluoride Chemical compound F[As](F)F JCMGUODNZMETBM-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229940006487 lithium cation Drugs 0.000 description 2
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical compound FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 2
- FFUQCRZBKUBHQT-UHFFFAOYSA-N phosphoryl fluoride Chemical compound FP(F)(F)=O FFUQCRZBKUBHQT-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910018928 (FSO2)2N Inorganic materials 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- 229910001558 CF3SO3Li Inorganic materials 0.000 description 1
- 241001517013 Calidris pugnax Species 0.000 description 1
- 229910005185 FSO3H Inorganic materials 0.000 description 1
- 229910005187 FSO3Li Inorganic materials 0.000 description 1
- 101000928408 Homo sapiens Protein diaphanous homolog 2 Proteins 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 description 1
- 229910019188 POF2 Inorganic materials 0.000 description 1
- 102100036469 Protein diaphanous homolog 2 Human genes 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GGYPIUANQNUBOE-UHFFFAOYSA-N n-(trifluoromethylsulfonyl)sulfamoyl fluoride Chemical compound FC(F)(F)S(=O)(=O)NS(F)(=O)=O GGYPIUANQNUBOE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention relates to a process for the industrial synthesis of acid imides salts and their anhydrous lithium imides salts, containing fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical, such as (FSO2)2NLi or (F2PO)2NLi.
Description
1. Field of the invention:
The invention relates to a process for the industrial synthesis of anhydrous lithium imides salts, containing fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical, such as (FSOz);NLi or (F2PO)2NLi.
The invention relates to a process for the industrial synthesis of anhydrous lithium imides salts, containing fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical, such as (FSOz);NLi or (F2PO)2NLi.
2. Description of the prior art:
Salts of low basicity anions are widely used in various industrial fields such as polymerization process, catalysis or batteries. In this last huge market application, lithium salt are one of the key component for electrolytes preparation.
Numerous lithium salts have been or are used in lithium batteries such as CF3SO3Li, LiBF4, LiPF6 or LiN (SO2CF3) 2. In addition to provide stable and conductive electrolytes when mixed with suitable organic solvents, lithium salts for batteries applications need to be obtain in an anhydrous state (typically with water content inferior to 1000 ppm and preferably inferior to 100 ppm).
LiPF6 is the main salt used in commercial lithium-ion ("Li-Ion") technology but it presents some drawbacks, especially a limited thermal stability which lowered the security of the battery and a poor stability to hydrolysis. On the other hand, salt such as LiN(SO2CF3)2 are stable up to 300 C and are not sensitive to hydrolysis but, due to cathodic corrosion of aluminum current collector, this salt is only used as an additive in Li-Ion technology.
A valuable compromise has been found by replacing CF3- radicals by fluorine atoms in LiN (S02CF3) 2= Indeed, LiN (SO2F) 2 imide is in particular more conductive and more stable on storage than LiPF6. Thus LiN(S02F)2 ("LiFSI") is a valuable substitute of at least LiPF6.
A few preparation process of LiFSI or its acid form are described. For example, concerning preparation of the acid, bis(fluorosulfonyl)imide (FSO2)2NH ("HFSI") is prepared by action of fluorosulfonic acid FSO3H with urea H2NC(O)NH2. Pure acid is then obtained by NaCl treatment of bulk media in dichloromethane followed by a distillation [Appel &
Eisenhauer, Chem. Ber. 95, 246-8, 1962]. However, toxicity and corrosive character of fluorosulfonic acid are major drawbacks of this synthesis. Moreover, yield of the reaction can fluctuate strongly for several experiments. An other process implied reaction of (C1SO,) zNH ("HC1SI") with AsF3. (FS02) 2NH is further isolated after treatment of bulk media by NaCl in dichloromethane [Ruff & Lustig, Inorg. Synth. 1968, 11, 138-43]. This process is of poor interest due to the high price of AsF3 and its toxicity.
From this acid, the preparation of its lithium salt is also difficult. Contrary to LiPF6, it is possible to prepare lithium salt of HFSI ("LiFSI") in water solution from the acid and a lithium source such as lithium carbonate. However, on drying, it is impossible to abstract the last molecules of water without decomposing major part of the lithium salt, this is specific to the lithium cation due to the high reticular energy of LiF. W095/26056 described a process to produce LiFSI
by reacting (FSO2)2NH and LiF in an aprotic solvent, such as acetonitrile. This process present several drawbacks, first the stability of the solvent to strong acid and it is also rather difficult to dry the obtained slurry to obtain pure LiFSI as there is a strong interaction between the lithium salt and acetonitrile solvent.
W002/053494 describe a process to prepare monovalent salt of HFSI by a "Halex" process in aprotic solvents. Such process is mainly designed to obtain the potassium salt of HFSI ("KFSI").
LiFSI salt preparation is also described but lead to the formation of a LiFSI salt containing large amount of impurity such as FSO3Li.
In the case of phosphoryl derivatives, the reaction of LiN ( SiMe3) 2 with POF3 lead to the formation of LiN ( POF2) Z after elimination of volatile Me3SiF [Fluck & Beuerle, Z. Anorg. Allg. Chem. 412(1), 65-70, 1975]. However, this process used costly silyl derivatives and toxic gaseous POF3.
So, it is clear this laboratory process is far from an industrial one's, moreover the final product contains undesirable Me3SiF complex with the salt which is difficult to remove. Moreover, this synthesis is of a limited scope.
Unfortunatly, it appears there is no satisfactory industrial process to produce anhydrous lithium imides salts, containing fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical such as (FSO2)2NLi or (F2PO)zNLi, and more generally to produce their acid precursors.
Salts of low basicity anions are widely used in various industrial fields such as polymerization process, catalysis or batteries. In this last huge market application, lithium salt are one of the key component for electrolytes preparation.
Numerous lithium salts have been or are used in lithium batteries such as CF3SO3Li, LiBF4, LiPF6 or LiN (SO2CF3) 2. In addition to provide stable and conductive electrolytes when mixed with suitable organic solvents, lithium salts for batteries applications need to be obtain in an anhydrous state (typically with water content inferior to 1000 ppm and preferably inferior to 100 ppm).
LiPF6 is the main salt used in commercial lithium-ion ("Li-Ion") technology but it presents some drawbacks, especially a limited thermal stability which lowered the security of the battery and a poor stability to hydrolysis. On the other hand, salt such as LiN(SO2CF3)2 are stable up to 300 C and are not sensitive to hydrolysis but, due to cathodic corrosion of aluminum current collector, this salt is only used as an additive in Li-Ion technology.
A valuable compromise has been found by replacing CF3- radicals by fluorine atoms in LiN (S02CF3) 2= Indeed, LiN (SO2F) 2 imide is in particular more conductive and more stable on storage than LiPF6. Thus LiN(S02F)2 ("LiFSI") is a valuable substitute of at least LiPF6.
A few preparation process of LiFSI or its acid form are described. For example, concerning preparation of the acid, bis(fluorosulfonyl)imide (FSO2)2NH ("HFSI") is prepared by action of fluorosulfonic acid FSO3H with urea H2NC(O)NH2. Pure acid is then obtained by NaCl treatment of bulk media in dichloromethane followed by a distillation [Appel &
Eisenhauer, Chem. Ber. 95, 246-8, 1962]. However, toxicity and corrosive character of fluorosulfonic acid are major drawbacks of this synthesis. Moreover, yield of the reaction can fluctuate strongly for several experiments. An other process implied reaction of (C1SO,) zNH ("HC1SI") with AsF3. (FS02) 2NH is further isolated after treatment of bulk media by NaCl in dichloromethane [Ruff & Lustig, Inorg. Synth. 1968, 11, 138-43]. This process is of poor interest due to the high price of AsF3 and its toxicity.
From this acid, the preparation of its lithium salt is also difficult. Contrary to LiPF6, it is possible to prepare lithium salt of HFSI ("LiFSI") in water solution from the acid and a lithium source such as lithium carbonate. However, on drying, it is impossible to abstract the last molecules of water without decomposing major part of the lithium salt, this is specific to the lithium cation due to the high reticular energy of LiF. W095/26056 described a process to produce LiFSI
by reacting (FSO2)2NH and LiF in an aprotic solvent, such as acetonitrile. This process present several drawbacks, first the stability of the solvent to strong acid and it is also rather difficult to dry the obtained slurry to obtain pure LiFSI as there is a strong interaction between the lithium salt and acetonitrile solvent.
W002/053494 describe a process to prepare monovalent salt of HFSI by a "Halex" process in aprotic solvents. Such process is mainly designed to obtain the potassium salt of HFSI ("KFSI").
LiFSI salt preparation is also described but lead to the formation of a LiFSI salt containing large amount of impurity such as FSO3Li.
In the case of phosphoryl derivatives, the reaction of LiN ( SiMe3) 2 with POF3 lead to the formation of LiN ( POF2) Z after elimination of volatile Me3SiF [Fluck & Beuerle, Z. Anorg. Allg. Chem. 412(1), 65-70, 1975]. However, this process used costly silyl derivatives and toxic gaseous POF3.
So, it is clear this laboratory process is far from an industrial one's, moreover the final product contains undesirable Me3SiF complex with the salt which is difficult to remove. Moreover, this synthesis is of a limited scope.
Unfortunatly, it appears there is no satisfactory industrial process to produce anhydrous lithium imides salts, containing fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical such as (FSO2)2NLi or (F2PO)zNLi, and more generally to produce their acid precursors.
3. Description of the invention:
To overcome those difficulties of salt preparation such as LiFSI, research has been done on various synthetic pathways, such as for example lithiation of the acid by alkyllithium in anhydrous alcane solvent. In fine, as a result of extensive investigations, a process based on anhydrous HF chemistry has been designed as the most suitable industrial synthetic procedure for anhydrous lithium imides salts, containing fluorosulfonyl (FSO?-) or fluorophosphoryl (F2PO-) electroattractor radical and characterized in that the fluorine atoms are covalently bond to the sulfur or phosphorus atoms, such as (FSO2) zNLi or (F2PO) 2NLi. As a result of research activities on lithium salt preparation, anhydrous HF chemistry has also proved effective to produce their acids counterparts.
So, the basic description of the process illustrated in the case of LiFSI is illustrated below:
FSO NH + LiF anhydrous HF
( 2)2 (FSO2)2NLi + HF
Indeed, the process to obtain an anhydrous lithium salt consist of an acid-base reaction between an acid imide, containing fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical, and a base LiM used as lithium cation source, preferably choose such as the HM species, formed during lithiation of the imide, is volatile as with LiCl or LiF which produce HCl and HF.
For example when operated at 180 C in an autoclave, this reaction lead to the formation of LiFSI of good purity.
The R&D activities on fluorinated imide lithium salt preparation as also allows to design an efficient process to obtain their acid counterparts from their chlorine derivatives in anhydrous HF, i.e from imides containing chlorosulfonyl (C1S02-) or chlorophosphoryl (Cl2PO-) electroattractor radical and characterized in that the chlorine atoms are covalently bond to the sulfur or phosphorus atoms, such as (C1SO2)2NH or (C12PO)2NH. This process is illustrated below in the case of bis(fluorosulfonyl)imide (HFSI):
(CISO2)2NH anhydrous HF (FSO2)2NH + HCI
Indeed, the fluorinated acid is obtained by a chlorine/fluorine exchange operated in anhydrous HF. It may be necessary to distillate the bulk media after reaction to obtain the pure acid.
The effectiveness of such reaction is non-obvious, it has been showed that when operated in an autoclave, the reaction proceed efficiently at temperature reaching or above 60 C. The anhydrous HF was then evaporated and the resulting product distillated to obtain pure HFSI.
It is also possible by a combination of both processes to obtain directly lithium salt such as LiFSI from the chlorine counterpart:
anhydrous HF --Jf (CISO 2)2NH + LiF (FSO2)2NLi + HCI
An other possibilities is to obtain directly lithium salt such as LiFSI from the lithiated chlorine counterpart:
anhydrous HF --Of (CISO2)2NL (FSO2)2NLi + HCI
The availability of acid imide containing (FSO2-) or (F~PO-) electroattractor radical from their chlorine equivalent (C1S02-) or (C12PO-) radical is particularly useful as it allows to extend the scope of available precursor to produce lithium imide salt containing (FSO2-) or (F2PO-) radical.
It has also been put in evidence that HFSI could be obtained from HC1SI by bulk reaction with KHF2.
The present invention is illustrated by the following examples, which are only used as an illustrative purpose without intended to provide any limitation for man of the art.
Preparation of HFSI: Reaction of 1 gr HN(SO2C1)2 with 4 gr HF
in an autoclave was done as various temperatures. Results are resumed in Table 1. It appears that an efficient Cl/F exchange could be performed. After evaporation of HF and distillation of bulk media, pure HFSI is obtained in a yield of at least 50%.
Time (hours) Temperature Yield 12 RT 0%
24 RT 0%
12 30 3-5%
12 50 7-10%
To overcome those difficulties of salt preparation such as LiFSI, research has been done on various synthetic pathways, such as for example lithiation of the acid by alkyllithium in anhydrous alcane solvent. In fine, as a result of extensive investigations, a process based on anhydrous HF chemistry has been designed as the most suitable industrial synthetic procedure for anhydrous lithium imides salts, containing fluorosulfonyl (FSO?-) or fluorophosphoryl (F2PO-) electroattractor radical and characterized in that the fluorine atoms are covalently bond to the sulfur or phosphorus atoms, such as (FSO2) zNLi or (F2PO) 2NLi. As a result of research activities on lithium salt preparation, anhydrous HF chemistry has also proved effective to produce their acids counterparts.
So, the basic description of the process illustrated in the case of LiFSI is illustrated below:
FSO NH + LiF anhydrous HF
( 2)2 (FSO2)2NLi + HF
Indeed, the process to obtain an anhydrous lithium salt consist of an acid-base reaction between an acid imide, containing fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical, and a base LiM used as lithium cation source, preferably choose such as the HM species, formed during lithiation of the imide, is volatile as with LiCl or LiF which produce HCl and HF.
For example when operated at 180 C in an autoclave, this reaction lead to the formation of LiFSI of good purity.
The R&D activities on fluorinated imide lithium salt preparation as also allows to design an efficient process to obtain their acid counterparts from their chlorine derivatives in anhydrous HF, i.e from imides containing chlorosulfonyl (C1S02-) or chlorophosphoryl (Cl2PO-) electroattractor radical and characterized in that the chlorine atoms are covalently bond to the sulfur or phosphorus atoms, such as (C1SO2)2NH or (C12PO)2NH. This process is illustrated below in the case of bis(fluorosulfonyl)imide (HFSI):
(CISO2)2NH anhydrous HF (FSO2)2NH + HCI
Indeed, the fluorinated acid is obtained by a chlorine/fluorine exchange operated in anhydrous HF. It may be necessary to distillate the bulk media after reaction to obtain the pure acid.
The effectiveness of such reaction is non-obvious, it has been showed that when operated in an autoclave, the reaction proceed efficiently at temperature reaching or above 60 C. The anhydrous HF was then evaporated and the resulting product distillated to obtain pure HFSI.
It is also possible by a combination of both processes to obtain directly lithium salt such as LiFSI from the chlorine counterpart:
anhydrous HF --Jf (CISO 2)2NH + LiF (FSO2)2NLi + HCI
An other possibilities is to obtain directly lithium salt such as LiFSI from the lithiated chlorine counterpart:
anhydrous HF --Of (CISO2)2NL (FSO2)2NLi + HCI
The availability of acid imide containing (FSO2-) or (F~PO-) electroattractor radical from their chlorine equivalent (C1S02-) or (C12PO-) radical is particularly useful as it allows to extend the scope of available precursor to produce lithium imide salt containing (FSO2-) or (F2PO-) radical.
It has also been put in evidence that HFSI could be obtained from HC1SI by bulk reaction with KHF2.
The present invention is illustrated by the following examples, which are only used as an illustrative purpose without intended to provide any limitation for man of the art.
Preparation of HFSI: Reaction of 1 gr HN(SO2C1)2 with 4 gr HF
in an autoclave was done as various temperatures. Results are resumed in Table 1. It appears that an efficient Cl/F exchange could be performed. After evaporation of HF and distillation of bulk media, pure HFSI is obtained in a yield of at least 50%.
Time (hours) Temperature Yield 12 RT 0%
24 RT 0%
12 30 3-5%
12 50 7-10%
4 110 24%
7 120 50%
7 120 50%
5 120 55%
2 130 55%
Table 1: Synthesis of HFSI in HF
Preparation of HFSI: Reaction of 1 gr HN(SO2C1)2 with 10 gr HF
in an autoclave was done as various temperatures. It appears that an efficient Cl/F exchange is performed at 60 C and above after 2 hours reaction. After evaporation of HF and distillation of bulk media, pure HFSI is obtained in a yield of at least 50%. The reaction was also performed in gas phase with a yield of at least 50%. The reaction was also performed with CF;SOzNHSOzCl and FSO2NHSO2C1, '9F NMR show fluorine pic relative to HFSI and CF3SO2NHSO2F after distillation of reactive media.
Preparation of FSI: Reaction of 10 gr HN(SO?-Cl)2 with 5 KHF2 equivalents was performed in bulk at 100-160 C in Teflon recipient under argon. After three hours, a sample of reaction media in CD3CN was analyzed by 19F NMR, showing a peak characteristic of the (FSO?)2N- anion.
Preparation of HFSI: Reaction of 10 gr HN(SO-9C1)2 with 4 gr HF
in an autoclave was done. Reaction mixture without chlorine traces were obtained at 65-70 C temperatures. After distillation, product obtained was identified by 19F NMR as HN(SO?F)2=HF adduct.
Preparation of LiFSI: Reaction of 1 gr of HN(SO2F)2 and an equimolar quantity of LiF in 5 ml of HF, at 180 C during 1 hour in an autoclave, gave nearly quantitative yield of LiFSI (> 99%) contaminated with a small amount of LiOSO2F - as determined by 19F NMR.
Preparation of LiFSI: Reaction of 1 gr HN(SO2C1)2 with 364 mg LiF in an autoclave containing 10 ml of HF was done at 120 C
during two hours. 15F NMR show a peak characteristic of the (FSO2)2N- anion and 'H NMR no peak characteristic of acidic proton in HFSI. The reaction was also performed with CF3SO2NHSO2C1, '9F NMR show fluorine pic relative to CF3SO2N SO2F
anions.
Preparation of LiFSI: Reaction of 1 gr LiN(SO2C1)2 with 400 mg LiF in an autoclave was done at 100 C during two hours. 19F NMR
show a peak characteristic of the (FSO2)2N anion.
2 130 55%
Table 1: Synthesis of HFSI in HF
Preparation of HFSI: Reaction of 1 gr HN(SO2C1)2 with 10 gr HF
in an autoclave was done as various temperatures. It appears that an efficient Cl/F exchange is performed at 60 C and above after 2 hours reaction. After evaporation of HF and distillation of bulk media, pure HFSI is obtained in a yield of at least 50%. The reaction was also performed in gas phase with a yield of at least 50%. The reaction was also performed with CF;SOzNHSOzCl and FSO2NHSO2C1, '9F NMR show fluorine pic relative to HFSI and CF3SO2NHSO2F after distillation of reactive media.
Preparation of FSI: Reaction of 10 gr HN(SO?-Cl)2 with 5 KHF2 equivalents was performed in bulk at 100-160 C in Teflon recipient under argon. After three hours, a sample of reaction media in CD3CN was analyzed by 19F NMR, showing a peak characteristic of the (FSO?)2N- anion.
Preparation of HFSI: Reaction of 10 gr HN(SO-9C1)2 with 4 gr HF
in an autoclave was done. Reaction mixture without chlorine traces were obtained at 65-70 C temperatures. After distillation, product obtained was identified by 19F NMR as HN(SO?F)2=HF adduct.
Preparation of LiFSI: Reaction of 1 gr of HN(SO2F)2 and an equimolar quantity of LiF in 5 ml of HF, at 180 C during 1 hour in an autoclave, gave nearly quantitative yield of LiFSI (> 99%) contaminated with a small amount of LiOSO2F - as determined by 19F NMR.
Preparation of LiFSI: Reaction of 1 gr HN(SO2C1)2 with 364 mg LiF in an autoclave containing 10 ml of HF was done at 120 C
during two hours. 15F NMR show a peak characteristic of the (FSO2)2N- anion and 'H NMR no peak characteristic of acidic proton in HFSI. The reaction was also performed with CF3SO2NHSO2C1, '9F NMR show fluorine pic relative to CF3SO2N SO2F
anions.
Preparation of LiFSI: Reaction of 1 gr LiN(SO2C1)2 with 400 mg LiF in an autoclave was done at 100 C during two hours. 19F NMR
show a peak characteristic of the (FSO2)2N anion.
Claims (39)
1) A process to prepare an anhydrous imide lithium salt LiX
obtained by reaction in anhydrous hydrogen fluoride (HF) of an acid imide HX, containing at least one fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical and characterized in that the fluorine atoms are covalently bond to the sulfur or phosphorus atoms, with a base LiM.
obtained by reaction in anhydrous hydrogen fluoride (HF) of an acid imide HX, containing at least one fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor radical and characterized in that the fluorine atoms are covalently bond to the sulfur or phosphorus atoms, with a base LiM.
2) A process according to claim 1 characterized in that the conjugated acid HM of LiM is volatile.
3) A process according to claim 1 characterized in that LiM is LiCl or/and LiF.
4) A process according to claim 1 characterized in that HX is HNZ1Z2 where Z1 is a fluorosulfonyl (FSO2-) or fluorophosphoryl (F2PO-) electroattractor and Z2 is an electroattractor radical with a Hammett parameter .sigma.p superior to 0.4, including FSO2-and F2PO- radicals.
5) A process according to claim 4 characterized in that Z2 is choose from FSO2-, F2PO- or C n F2n+1SO2- with n = 1-10.
6) A process according to claim 5 characterized in that 1<=n<=4.
7) A process according to claim 4 characterized in that HX is (FSO2)2NH.
8) A process according to claim 1 characterized in that the reaction is performed between 25 and 200°C.
9) A process according to claim 8 characterized in that the reaction is performed between 50 and 150°C.
10) A process according to claim 4 characterized in that the reaction is performed in an autoclave.
11) A process to prepare an acid imide HX' obtained by a chlorine/fluorine exchange, perform in and by anhydrous HF, from an acid imide HX', containing at least one chlorosulfonyl (ClSO2-) or chlorophosphoryl (Cl2PO-) electroattractor radical and characterized in that the chlorine atoms are covalently bond to the sulfur or phosphorus atoms.
12) A process according to claim 11 characterized in that HX' is HNZ'1Z'2 where Z'1 is a chlorosulfonyl (ClSO2-) or chlorophosphoryl (C12PO-) electroattractor and Z'2 is an electroattractor radical with a Hammett parameter .sigma.p superior to 0.4, including C1SO2- and Cl2PO- radicals.
13) A process according to claim 12 wherein Z'2 is C1SO2-, C12PO- or C n F2+1SO2- with n = 1-10.
14) A process according to claim 12 where HX' is (ClSO2)2NH.
15) A process according to claim 12 characterized in that the reaction is performed between 25 and 200°C.
16) A process according to claim 15 wherein the reaction is performed between 50 and 150°C.
17) A process according to claim 12 characterized in that the reaction is performed in an autoclave.
18) A process according to claim 12 characterized in that the reaction is performed in gaseous phase.
19) A process according to claim 12 characterized in that the reaction media is distillate to obtain pure HX acid.
20) A process to prepare an anhydrous lithium imide salt LiX' obtained by a chlorine/fluorine exchange and H+/Li+ exchange, perform in and by anhydrous HF in presence of a lithium salt LiM, from an acid imide HX', containing at least one chlorosulfonyl (ClSO2-) or chlorophosphoryl (Cl2PO-) electroattractor radical and characterized in that the chlorine atoms are covalently bond to the sulfur or phosphorus atoms.
21) A process according to claim 20 characterized in that the conjugated acid HM of LiM is volatile.
22) A process according to claim 21 characterized in that LiM
is LiCl or/and LiF.
is LiCl or/and LiF.
23) A process according to claim 20 characterized in that LiM
is in equivalent molar quantity of HX'.
is in equivalent molar quantity of HX'.
24) A process according to claim 20 characterized in that HX' is HNZ'1Z'2 where Z'1 is a chlorosulfonyl (C1S02-) or chlorophosphoryl (C12PO-) electroattractor and Z'2 is an electroattractor radical with a Hammett parameter .sigma.p superior to 0.4, including C1SO2- and Cl2PO- radicals.
25) A process according to claim 24 characterized in that Z'2 is choose from ClS02-, Cl2P0- or C n F2n+1SO2- with n = 1-10.
26) A process according to claim 25 characterized in that 1<=n<=4.
27) A process according to claim 24 characterized in that HX' is (ClSO2) 2NH.
28) A process according to claim 20 characterized in that the reaction is performed between 25 and 200°C.
29) A process according to claim 28 characterized in that the reaction is performed between 50 and 150°C.
30) A process according to claim 24 characterized in that the reaction is performed in an autoclave.
31) A process to prepare an acid imide HX' obtained by a chlorine/fluorine exchange, perform by KHF2, from an acid imide HX', containing at least one chlorosulfonyl (C1SO2-) or chlorophosphoryl (Cl2PO-) electroattractor radical and characterized in that the chlorine atoms are covalently bond to the sulfur or phosphorus atoms.
32) A process according to claim 31 characterized in that HX' is HNZ'1Z'2 where Z'i is a chlorosulfonyl (C1S02-) or chlorophosphoryl (C12PO-) electroattractor and Z'2 is an electroattractor radical with a Hammett parameter .sigma.P superior to 0.4, including C1SO2- and C12PO- radicals.
33) A process according to claim 32 wherein Z'2 is C1S02-, C12PO- or C n F2n+1S02- with n = 1-10.
34) A process according to claim 32 where HX' is (C1SO2)2NH.
35) A process according to claim 32 characterized in that the reaction is performed between 25 and 200°C in bulk.
36) A process according to claim 35 wherein the reaction is performed between 50 and 150°C in bulk.
36) A process according to claim 32-36 characterized in that the reaction is performed in presence of a solvent.
36) A process according to claim 32-36 characterized in that the reaction is performed in presence of a solvent.
37) A process according to claim 32 characterized in that the reaction is performed in an autoclave.
38) A process according to claim 32 characterized in that the reaction is performed in gaseous phase.
39) A process according to claim 32 characterized in that the reaction media is distillate to obtain pure HX acid.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2527802 CA2527802A1 (en) | 2005-12-12 | 2005-12-12 | Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent |
| PCT/FR2006/002712 WO2007068822A2 (en) | 2005-12-12 | 2006-12-12 | Sulphonyl-1,2,4-triazole salts |
| US12/097,148 US7919629B2 (en) | 2005-12-12 | 2006-12-12 | Sulphonyl-1,2,4-triazole salts |
| US13/079,476 US20110178306A1 (en) | 2005-12-12 | 2011-04-04 | Sulphonyl-1,2,4-Triazole Salts |
| US13/478,728 US20120232285A1 (en) | 2005-12-12 | 2012-05-23 | Sulfonyl-1,2,4-triazole salts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2527802 CA2527802A1 (en) | 2005-12-12 | 2005-12-12 | Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2527802A1 true CA2527802A1 (en) | 2007-06-12 |
Family
ID=38162328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2527802 Abandoned CA2527802A1 (en) | 2005-12-12 | 2005-12-12 | Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2527802A1 (en) |
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