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
- Publication number
- CA2527802A1 CA2527802A1 CA 2527802 CA2527802A CA2527802A1 CA 2527802 A1 CA2527802 A1 CA 2527802A1 CA 2527802 CA2527802 CA 2527802 CA 2527802 A CA2527802 A CA 2527802A CA 2527802 A1 CA2527802 A1 CA 2527802A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- reaction
- electroattractor
- radical
- anhydrous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
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) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2975684A1 (en) * | 2011-05-24 | 2012-11-30 | Arkema France | PROCESS FOR THE PREPARATION OF BIS (FLUOROSULFONYL) IMIDURE OF LITHIUM OR SODIUM |
| WO2014036814A1 (en) * | 2012-09-10 | 2014-03-13 | 江苏华盛精化工股份有限公司 | Method for preparing bis(fluorosulfonyl)imide |
| WO2015012897A1 (en) | 2013-07-26 | 2015-01-29 | Boulder Ionics Corporation | Synthesis of hydrogen bis(fluorosulfonyl)imide |
| JP2016204218A (en) * | 2015-04-24 | 2016-12-08 | ステラケミファ株式会社 | Manufacturing method of fluorosulfonylimide compound |
| WO2017080831A1 (en) * | 2015-11-13 | 2017-05-18 | Lonza Ltd | Method for the preparation of bis(fluorosulfonyl)-imide and of its salts |
| JP2018035060A (en) * | 2016-08-30 | 2018-03-08 | 森田化学工業株式会社 | Lithium bis(fluorosulfonyl) imide composition |
| JP2018035059A (en) * | 2016-08-30 | 2018-03-08 | 森田化学工業株式会社 | Lithium bis(fluorosulfonyl) imide composition |
| US9947967B2 (en) | 2009-11-27 | 2018-04-17 | Nippon Shokubai Co., Ltd. | Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt |
| KR20190002543A (en) | 2016-05-26 | 2019-01-08 | 모리타 가가쿠 고교 가부시키가이샤 | Method for producing bis (fluorosulfonyl) imide alkali metal salt and bis (fluorosulfonyl) imide alkali metal salt composition |
| KR20190003708A (en) * | 2016-05-27 | 2019-01-09 | 가부시기가이샤 닛뽕쇼꾸바이 | Method for producing alkali metal salt of bis (fluorosulfonyl) imide |
| KR20190003710A (en) | 2016-05-27 | 2019-01-09 | 가부시기가이샤 닛뽕쇼꾸바이 | Method for producing bis (fluorosulfonyl) imide alkali metal salt and method for producing non-aqueous liquid electrolyte |
| KR20190006524A (en) | 2017-02-08 | 2019-01-18 | 모리타 가가쿠 고교 가부시키가이샤 | Method for producing bis (fluorosulfonyl) imide metal salt and corresponding metal salt |
| US20190161356A1 (en) * | 2017-11-28 | 2019-05-30 | Nippon Shokubai Co., Ltd. | Lithium bis(fluorosulfonyl)imide composition |
| EP3782982A1 (en) | 2019-08-22 | 2021-02-24 | Fujian Yongjing Technology Co., Ltd. | Process for the synthesis of fluorinated conductive salts for lithium ion batteries |
| WO2021171948A1 (en) | 2020-02-27 | 2021-09-02 | 株式会社日本触媒 | Composition, electrolytic solution material, and electrolytic solution |
| WO2023169842A1 (en) | 2022-03-07 | 2023-09-14 | Specialty Operations France | Method for producing alkali sulfonyl imide salts |
| WO2023169843A1 (en) | 2022-03-07 | 2023-09-14 | Specialty Operations France | Method for producing lithium fluorosulfonyl imide salts |
| WO2024002897A1 (en) | 2022-07-01 | 2024-01-04 | Specialty Operations France | Method for fluorinating hydrogen bis(chlorosulfonyl)imide in gas phase |
| WO2024061956A1 (en) | 2022-09-22 | 2024-03-28 | Specialty Operations France | Method for producing alkali sulfonyl imide salts |
-
2005
- 2005-12-12 CA CA 2527802 patent/CA2527802A1/en not_active Abandoned
Cited By (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2505551B2 (en) † | 2009-11-27 | 2022-03-09 | Nippon Shokubai Co., Ltd. | Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt |
| EP2505551B1 (en) | 2009-11-27 | 2018-07-25 | Nippon Shokubai Co., Ltd. | Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt |
| US9947967B2 (en) | 2009-11-27 | 2018-04-17 | Nippon Shokubai Co., Ltd. | Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt |
| WO2012160280A3 (en) * | 2011-05-24 | 2013-02-28 | Arkema France | Method for producing lithium or sodium bis(fluorosulfonyl)imidide |
| EP3620433A1 (en) * | 2011-05-24 | 2020-03-11 | Arkema France | Lithium bis(fluorosulfonyl)imide |
| US9394172B2 (en) | 2011-05-24 | 2016-07-19 | Arkema France | Process for the preparation of lithium or sodium bis(fluorosulphonyl)imide |
| US9440852B2 (en) | 2011-05-24 | 2016-09-13 | Arkema France | Method for producing lithium or sodium bis(fluorosulfonyl)imide |
| US10547084B2 (en) | 2011-05-24 | 2020-01-28 | Arkema France | Process for the preparation of lithium or sodium bis(fluorosulphonyl)imide |
| FR2975684A1 (en) * | 2011-05-24 | 2012-11-30 | Arkema France | PROCESS FOR THE PREPARATION OF BIS (FLUOROSULFONYL) IMIDURE OF LITHIUM OR SODIUM |
| WO2014036814A1 (en) * | 2012-09-10 | 2014-03-13 | 江苏华盛精化工股份有限公司 | Method for preparing bis(fluorosulfonyl)imide |
| CN103663393A (en) * | 2012-09-10 | 2014-03-26 | 江苏华盛精化工股份有限公司 | Preparation method of difluoro lithium sulfimide |
| CN103663393B (en) * | 2012-09-10 | 2015-09-30 | 江苏华盛精化工股份有限公司 | The preparation method of two fluoro sulfimide lithium |
| WO2015012897A1 (en) | 2013-07-26 | 2015-01-29 | Boulder Ionics Corporation | Synthesis of hydrogen bis(fluorosulfonyl)imide |
| EP3024779B1 (en) | 2013-07-26 | 2019-07-17 | Coorstek Fluorochemicals, Inc. | Synthesis of hydrogen bis(fluorosulfonyl)imide |
| EP3024779A4 (en) * | 2013-07-26 | 2017-03-15 | Coorstek Fluorochemicals, Inc. | Synthesis of hydrogen bis(fluorosulfonyl)imide |
| JP2016204218A (en) * | 2015-04-24 | 2016-12-08 | ステラケミファ株式会社 | Manufacturing method of fluorosulfonylimide compound |
| WO2017080831A1 (en) * | 2015-11-13 | 2017-05-18 | Lonza Ltd | Method for the preparation of bis(fluorosulfonyl)-imide and of its salts |
| KR102328454B1 (en) * | 2016-05-26 | 2021-11-18 | 가부시키가이샤 닛폰 쇼쿠바이 | Method for producing alkali metal salt of bis(fluorosulfonyl)imide and composition of alkali metal salt of bis(fluorosulfonyl)imide |
| KR20190002543A (en) | 2016-05-26 | 2019-01-08 | 모리타 가가쿠 고교 가부시키가이샤 | Method for producing bis (fluorosulfonyl) imide alkali metal salt and bis (fluorosulfonyl) imide alkali metal salt composition |
| CN109311669A (en) * | 2016-05-26 | 2019-02-05 | 森田化学工业株式会社 | The manufacturing method of double fluorine sulfimide alkali metal salts and double fluorine sulfimide alkali metal salt compositions |
| CN109311669B (en) * | 2016-05-26 | 2022-04-19 | 株式会社日本触媒 | Method for producing alkali metal salt of bis (fluorosulfonyl) imide, and alkali metal salt composition of bis (fluorosulfonyl) imide |
| EP3466871A4 (en) * | 2016-05-26 | 2019-10-23 | Nippon Shokubai Co., Ltd. | Method for producing bis(fluorosulfonyl)imide alkali metal salt and bis(fluorosulfonyl)imide alkali metal salt composition |
| CN109415209A (en) * | 2016-05-27 | 2019-03-01 | 株式会社日本触媒 | The preparation method of two (fluorosulfonyl) imine alkali metal salts |
| CN109415209B (en) * | 2016-05-27 | 2022-09-27 | 株式会社日本触媒 | Process for producing bis (fluorosulfonyl) imide alkali metal salt |
| JPWO2017204303A1 (en) * | 2016-05-27 | 2019-03-22 | 株式会社日本触媒 | Process for producing bis (fluorosulfonyl) imide alkali metal salt |
| EP3466873A4 (en) * | 2016-05-27 | 2019-10-23 | Nippon Shokubai Co., Ltd. | Method for producing bis(fluorosulfonyl)imide alkali metal salt |
| EP3466872A4 (en) * | 2016-05-27 | 2019-10-30 | Nippon Shokubai Co., Ltd. | Method for producing bis(fluorosulfonyl)imide alkali metal salt and method for producing non-aqueous electrolytic solution |
| KR20190003708A (en) * | 2016-05-27 | 2019-01-09 | 가부시기가이샤 닛뽕쇼꾸바이 | Method for producing alkali metal salt of bis (fluorosulfonyl) imide |
| KR20190003710A (en) | 2016-05-27 | 2019-01-09 | 가부시기가이샤 닛뽕쇼꾸바이 | Method for producing bis (fluorosulfonyl) imide alkali metal salt and method for producing non-aqueous liquid electrolyte |
| US10829377B2 (en) | 2016-05-27 | 2020-11-10 | Nippon Shokubai Co., Ltd. | Method for producing bis(fluorosulfonyl)imide alkali metal salt and method for producing non aqueous electrolytic solution |
| KR102208181B1 (en) * | 2016-05-27 | 2021-01-28 | 가부시기가이샤 닛뽕쇼꾸바이 | Method for producing bis(fluorosulfonyl)imide alkali metal salt |
| JP2018035059A (en) * | 2016-08-30 | 2018-03-08 | 森田化学工業株式会社 | Lithium bis(fluorosulfonyl) imide composition |
| JP2018035060A (en) * | 2016-08-30 | 2018-03-08 | 森田化学工業株式会社 | Lithium bis(fluorosulfonyl) imide composition |
| KR102231961B1 (en) | 2017-02-08 | 2021-03-25 | 가부시키가이샤 닛폰 쇼쿠바이 | Bis(fluorosulfonyl)imide metal salt and method for producing the metal salt |
| US11097949B2 (en) | 2017-02-08 | 2021-08-24 | Morita Chemical Industries Co., Ltd. | Bis(fluorosulfonyl) imide metal salt and method for preparing same |
| KR20190006524A (en) | 2017-02-08 | 2019-01-18 | 모리타 가가쿠 고교 가부시키가이샤 | Method for producing bis (fluorosulfonyl) imide metal salt and corresponding metal salt |
| US20190161356A1 (en) * | 2017-11-28 | 2019-05-30 | Nippon Shokubai Co., Ltd. | Lithium bis(fluorosulfonyl)imide composition |
| EP3782982A1 (en) | 2019-08-22 | 2021-02-24 | Fujian Yongjing Technology Co., Ltd. | Process for the synthesis of fluorinated conductive salts for lithium ion batteries |
| WO2021171948A1 (en) | 2020-02-27 | 2021-09-02 | 株式会社日本触媒 | Composition, electrolytic solution material, and electrolytic solution |
| WO2023169842A1 (en) | 2022-03-07 | 2023-09-14 | Specialty Operations France | Method for producing alkali sulfonyl imide salts |
| WO2023169843A1 (en) | 2022-03-07 | 2023-09-14 | Specialty Operations France | Method for producing lithium fluorosulfonyl imide salts |
| WO2024002897A1 (en) | 2022-07-01 | 2024-01-04 | Specialty Operations France | Method for fluorinating hydrogen bis(chlorosulfonyl)imide in gas phase |
| WO2024061956A1 (en) | 2022-09-22 | 2024-03-28 | Specialty Operations France | Method for producing alkali sulfonyl imide salts |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2527802A1 (en) | Synthesis of anhydrous imides lithium salts containing fluorosulfonyl or fluorophosphoryl substituent | |
| CN107986248B (en) | Preparation method of bis (fluorosulfonyl) imide | |
| US10128525B2 (en) | Preparation of imides containing a fluorosulfonyl group | |
| CN105826596B (en) | Preparation method of ionic liquid and secondary battery | |
| EP3381923B1 (en) | Novel method for preparing lithium bis(fluorosulfonyl)imide | |
| CN106044728B (en) | A kind of preparation method of imidodisulfuryl fluoride lithium salt | |
| JP4616925B2 (en) | Method for producing difluorophosphate | |
| Xu et al. | A fusible orthoborate lithium salt with high conductivity in solutions | |
| JP6226643B2 (en) | Method for producing lithium difluorophosphate | |
| JP4560132B2 (en) | Method for producing difluorophosphate | |
| CA2619346A1 (en) | Process for preparing sulfonylimides and derivatives thereof | |
| CN108456155A (en) | The method for being used to prepare the imide salts containing fluorosulfonyl group | |
| CN109264683B (en) | Method for extracting and purifying bis (fluorosulfonyl) imide | |
| WO2018157240A1 (en) | Method for preparing compounds comprising a fluorosulfonyl group, and novel reagents enabling such chemical reactions | |
| WO2006118232A1 (en) | Ionic liquid containing phosphonium ion and method for producing same | |
| CN110407184B (en) | Preparation method of bis (fluorosulfonyl) imide alkali metal salt | |
| KR100971065B1 (en) | Method for producing electrolyte solution for lithium ion battery and lithium ion battery using same | |
| WO2016081525A1 (en) | Concentrated electrolyte solution | |
| CN113148971A (en) | Preparation method of lithium difluorophosphate | |
| CN112707418A (en) | Preparation method of lithium hexafluorophosphate | |
| JP6199117B2 (en) | Method for producing difluorophosphate | |
| JP2016008145A (en) | Lithium fluorosulfate and solution containing the same, and method for producing the same | |
| KR20210092226A (en) | Purified lithium bis(fluorosulfonyl)imide (LiFSI) product, process for purification of crude LiFSI, and use of purified LiFSI product | |
| AU2019244870A1 (en) | Production of lithium hexafluorophosphate | |
| CN114604832A (en) | Preparation method of lithium bis (fluorosulfonyl) imide and application of lithium bis (fluorosulfonyl) imide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |