CA2959745A1 - Preparation process for compounds including a fluorosulfonyl group, and new reactants allowing such chemical reactions - Google Patents
Preparation process for compounds including a fluorosulfonyl group, and new reactants allowing such chemical reactions Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
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- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C07—ORGANIC CHEMISTRY
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/34—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfuric acids
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- C07—ORGANIC CHEMISTRY
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H01M10/0566—Liquid materials
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- H01—ELECTRIC ELEMENTS
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- 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
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- 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
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- H01M10/0569—Liquid materials characterised by the solvents
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Abstract
La demande concerne un composé de formule : (Voir Formule si Haut) Plusieurs utilisations diverses de ce composé sont décrites afin de préparer différents composés. Par exemple, ce composé permet de greffer un groupement fluorosulfonyle sur une molécule. Le procédé de synthèse de ce composé est également décrit.The application relates to a compound of formula: (see Formula if High) Several diverse uses of this compound are described in order to prepare different compounds. For example, this compound makes it possible to graft a fluorosulfonyl group onto a molecule. The process for synthesizing this compound is also described.
Description
a a PROCÉDÉS DE PRÉPARATION DE COMPOSÉS COMPRENANT UN
GROUPE FLUOROSULFONYLE, ET NOUVEAUX RÉACTIFS
PERMETTANT DE TELLES RÉACTIONS CHIMIQUES
DOMAINE DE LA DIVULGATION
[0001] Les batteries Li-Ion et Lithium-Polymère (LMP) ont des propriétés supérieures à toutes les autres batteries. Tel qu'une densité
d'énergie très élevée, une faible autodécharge combinée avec un effet mémoire négligeable. at at METHODS FOR PREPARING COMPOUNDS COMPRISING A
FLUOROSULFONYL GROUP, AND NEW REAGENTS
PERMITTING SUCH CHEMICAL REACTIONS
FIELD OF DISCLOSURE
Li-Ion and Lithium-Polymer (LMP) batteries have some properties superior to all other batteries. Such as a density very high energy, low self-discharge combined with an effect negligible memory.
[0002] Un liquide ionique ou bien un sel-fondu à
température ambiante est une série de solvants polaires ayant une très faible viscosité, une conductivité ionique très élevée et une stabilité thermique et électrochimique élevée. Ces sels sont très recherchés en tant qu'électrolytes dans les dispositifs électrochimiques. [0002] An ionic liquid or a salt-melted to temperature ambient is a series of polar solvents with a very low viscosity, very high ionic conductivity and thermal stability and high electrochemical. These salts are highly sought after as electrolytes in electrochemical devices.
[0003] Les différentes combinaisons d'anions et de cations donnent des variations illimitées de sel et permet d'engendrer des solvants ayant des propriétés physico-chimiques sur mesure. The various combinations of anions and cation give unlimited variations in salt and can generate solvents with specific physicochemical properties.
[0004] De plus, ces liquides ioniques sont :
= Non-volatile et = Très résistants aux flammes. [0004] In addition, these ionic liquids are:
= Non-volatile and = Very flame resistant.
[0005] Toutes ces caractéristiques les rendent fort attrayants pour remplacer les solvants organiques habituels dans les batteries Li-Ion jugés très peu sécuritaires. [0005] All these characteristics make them strong attractive for replace the usual organic solvents in Li-Ion batteries considered very unsafe.
[0006] La réaction exothermique engendrée à la première étape de décomposition des électrolytes organiques dans les piles au lithium, implique une décomposition rapide de l'électrolyte catalysée par les matériaux d'électrodes de la pile et accélérée avec la chaleur. En outre, ces électrolytes contiennent des solvants organiques très volatils, comme le PC et le DMC, la pression intérieure de la pile peut, à tout moment, augmenter et faire exploser la pile. Si la pile est ouverte à l'air, ces solvants jouent le rôle d'un combustible et même si la batterie reste =
=
fermée les matériaux d'électrodes catalysent une réaction de décomposition avec l'électrolyte si la température atteint 200 C suite à
un court-circuit ou une collision. The exothermic reaction generated at the first stage decomposition of organic electrolytes in lithium batteries, involves rapid decomposition of the electrolyte catalyzed by the battery electrode materials and accelerated with heat. In addition, these electrolytes contain very volatile organic solvents, Like the PC and the DMC, the internal pressure of the battery can, at any moment, increase and blow up the stack. If the battery is open to air, these solvents play the role of a fuel and even if the battery remains =
=
closed electrode materials catalyze a reaction of decomposition with the electrolyte if the temperature reaches 200 C following a short circuit or a collision.
[0007] De ce fait, il est très urgent de remplacer les électrolytes organiques volatiles et inflammables par un autre system plus sécuritaire.
Les Électrolytes Liquides Ioniques (IL's) 1- IL avec l'anion Chloroaluminate [0007] As a result, it is very urgent to replace electrolytes Volatile organic substances and flammable by another system more safe.
Ionic Liquid Electrolytes (IL's) 1- IL with Chloroaluminate Anion
[0008] C'est la première famille de sel fondu qui a été étudiée pour les applications en batteries Li-ion. Néanmoins, ces sels sont très sensibles à l'air, très corrosifs et leur utilisation reste très problématique à cause de leur instabilité cathodique vis-à-vis du Lithium électrode.
2- IL des Alkylimidazolium et flluorosulfonimides. This is the first molten salt family that has been studied for applications in Li-ion batteries. Nevertheless, these salts are very sensitive to air, very corrosive and their use remains very problematic because of their cathodic instability vis-à-vis the lithium electrode.
2- IL Alkylimidazolium and Flluorosulfonimides.
[0009] Plusieurs liquides ioniques avec des anions fluorés sont à
la fois liquides à température ambiante et ayant une bonne stabilité
anodique et très peu sensible à l'humidité, combinée à une très faible viscosité (e.g. EMI TFSI). Des caractéristiques idéales pour les applications en batteries Li-ion. Toutefois, ces sels subissent une décomposition cathodique dans la région du potentiel positif vis-à-vis de Li/Li'. De plus, une réaction d'intercalation irréversible des carbocations à l'intérieur des couches de graphite vers 0,5 V vs. Li/Li+.
C'est la raison essentielle pour laquelle les chercheurs n'ont jamais pu fabriquer des batteries Li-ion avec des liquides ioniques purs et sans additifs organiques volatiles et corrosifs.
3- Pourquoi les électrolytes à base de FSI (bis(fluorosulfonyl)imide)? [0009] Several ionic liquids with anions fluorinated both liquid at room temperature and having good stability anodic and very insensitive to moisture, combined with a very low viscosity (eg EMI TFSI). Ideal characteristics for applications in Li-ion batteries. However, these salts undergo a cathodic decomposition in the region of the positive potential vis-à-vis Lili'. In addition, an irreversible intercalation reaction of carbocations inside the layers of graphite towards 0.5 V vs. Li / Li +.
This is the main reason why researchers have never been able to manufacture Li-ion batteries with pure ionic liquids and without volatile and corrosive organic additives.
3- Why electrolytes based on FSI (bis (fluorosulfonyl) imide)?
[0010] Ishikawa et al (Journal of Power Sources 162 (2006) 658-662) ont clairement démontré que les liquides ioniques à base de FSI, brevet détenu par HydroQuébec, sont les seuls sels fondus connus permettant de fabriquer des batteries Li-ion avec des liquides ioniques pur avec de très bons résultats. Ishikawa et al (Journal of Power Sources 162 (2006) 658-662) have clearly demonstrated that ionic liquids based on FSI, patent held by HydroQuébec, are the only known molten salts making it possible to manufacture Li-ion batteries with ionic liquids pure with very good results.
[0011] Cet anion est le précurseur des sels liquides très peu visqueux très conducteurs et très stable. De plus, l'anion FSI forme une couche de passivation sur les électrodes et prévient la réaction indésirable des liquides ioniques classiques (l'intercalation irréversible des carbocations à l'intérieur des électrodes). This anion is the precursor of very little liquid salts very conductive viscous and very stable. In addition, the FSI anion forms a passivation layer on the electrodes and prevents the reaction of conventional ionic liquids (irreversible intercalation carbocations inside the electrodes).
[0012] La FIG. 1 montre l'absence totale de la réaction d'intercalation courante des sels fondus classiques.
Méthodes De Synthèse Connues De L'anion FSI [0012] FIG. 1 shows the total absence of the reaction common intercalation of conventional melted salts.
Known Synthesis Methods of the FSI Anion
[0013] L'anion FSI est très recherché depuis plusieurs années.
Néanmoins, sa préparation est très difficile et aucune méthode connue ne permet d'en produire industriellement:
L'action de l'acide FSO3H sur l'urée (Chem. Ber., 1962, 95, 246-248.) o Fso3H + H2N¨I-L-NH2 ___________________________ HFSI
bp 166 C - NH4S03F bp 170 C
-c 02 The FSI anion has been very popular for several years.
Nevertheless, its preparation is very difficult and no known method does not allow to produce industrially:
The action of FSO3H acid on urea (Chem Ber, 1962, 95, 246-248.) o Fso3H + H2N¨IL-NH2 ___________________________ HFSI
bp 166 C - NH4S03F bp 170 C
-c 02
[0014] Une difficulté est rencontrée i.e. l'acide fluorosulfonique est très corrosif, très cher et peu disponible et il a quasiment le même point d'ébullition que le HFSI, ce qui rend impossible la purification de ce dernier.
=
Protonation de N-Sulfonyl trichlorophosphazene (lnorganic Chemistry Communications, 1999, 2(6), 261-264) AsF3 FSO3H + Cio2S¨N=F03 ___ HFSI
Difficultés :
= L'utilisation de l'acide fluorosulfonique.
= La synthèse des trichlorophosphazene compliquée et très onéreuse.
= L'utilisation du fluorure d'arsénique extrêmement toxique = Faible rendement La réaction d'amidosulfurique avec l'acide chlorosulfurique (Z. Anorg.
Allg. Chem. 2005, 631,55-59) 1) CISO3H
2) 6KF
H2N-S03H SOCl2 ____________ - KFSI
- 2HCI, -S02, -HF
Difficultés :
= Réactifs corrosifs et dispendieux.
= Temps et température élevées. (Plusieurs jours de 80 à 180 C) = Réaction hétérogène (réactif insoluble) = Très faible rendement = II est très difficile de transformer le KFSI en LiFSI A difficulty is encountered ie the fluorosulfonic acid is very corrosive, very expensive and not very available and it has almost the same point boiling point as the HFSI, which makes it impossible to purify this latest.
=
Protonation of N-Sulfonyl Trichlorophosphazene (Inorganic Chemistry Communications, 1999, 2 (6), 261-264) AsF3 FSO3H + Cio2S¨N = F03 ___ HFSI
Difficulty:
= The use of fluorosulfonic acid.
The synthesis of trichlorophosphazene complicated and very expensive.
= The use of extremely toxic arsenic fluoride = Low efficiency The reaction of amidosulfuric acid with chlorosulfuric acid (Z. Anorg.
Allg. Chem. 2005, 631.55-59) 1) CISO3H
2) 6KF
H2N-S03H SOCl2 ____________ - KFSI
- 2HCI, -S02, -HF
Difficulty:
= Corrosive and expensive reagents.
= High time and temperature. (Several days from 80 to 180 C) = Heterogeneous reaction (insoluble reagent) = Very low efficiency = It is very difficult to transform KFSI into LiFSI
[0015] Il serait donc souhaitable d'obtenir un procédé
de synthèse et/ou un nouveau réactif chimique qui permettraient d'éviter ou de diminuer les inconvénients des méthodes de l'art antérieur.
SOMMAIRE DE LA DIVULGATION [0015] It would therefore be desirable to obtain a method of synthesis and / or a new chemical reagent that would prevent or to reduce the disadvantages of the methods of the prior art.
SUMMARY OF DISCLOSURE
[0016] La présente divulgation concerne un composé de formule =
=
II
F-S-N
I I The present disclosure relates to a compound of formula =
=
II
FSN
II
[0017] La présente divulgation concerne également l'utilisation du composé de formule ci-dessus dans la préparation d'un composé
comprenant un groupe fluorosulfonyle :
o The present disclosure also relates to the use of compound of formula above in the preparation of a compound comprising a fluorosulfonyl group o
[0018] La présente divulgation concerne également un procédé
de préparation du composé de formule :
II N
F-S-N
I I
dans lequel on fait réagir S02F2 avec l'imidazole, en présence d'une base forte. The present disclosure also relates to a process for preparing the compound of formula:
II N
FSN
II
wherein SO 2 F 2 is reacted with imidazole in the presence of a strong base.
[0019] La présente divulgation concerne également un procédé
de préparation du composé de formule :
.+
I II I
F-S-N-S-F
II II
dans lequel on fait réagir LiN H2 avec II
F-S-N
I I The present disclosure also relates to a process for preparing the compound of formula:
. +
I II I
FSNSF
II II
in which LiN H2 is reacted with II
FSN
II
[0020] La présente divulgation concerne également un procédé
de préparation du composé de formule :
0 Li+
II
F-S-N ______________________________ II
dans lequel on fait réagir et II
F-S-N
I I The present disclosure also relates to a method of for preparing the compound of formula:
0 Li +
II
FSN ______________________________ II
in which one makes react and II
FSN
II
[0021] La présente divulgation concerne également un procédé
de préparation du composé de formule :
I I Li F-S_ I I
dans lequel on fait réagir CH2(CN)2 et II
F-S-N
I I
= The present disclosure also relates to a method of for preparing the compound of formula:
II Li F-S_ II
in which one makes react CH2 (CN) 2 and II
FSN
II
=
[0022] La présente divulgation concerne également un procédé
de préparation du composé de formule :
0 Li 0 F
II-I I
F-S-N---S _________________________________________________ I I I I
dans lequel on fait réagir et II
F-S-N
I I The present disclosure also relates to a process for preparing the compound of formula:
0 Li 0 F
II-I I
FSN --- S _________________________________________________ IIII
in which one makes react and II
FSN
II
[0023] La présente divulgation concerne également un procédé
de préparation du composé de formule :
FN
,,D
dans lequel on fait réagir Mg+13r et II
F-S-N
I I The present disclosure also relates to a process for preparing the compound of formula:
FN
,, D
in which one makes react Mg + 13r and II
FSN
II
[0024] La présente divulgation concerne également un procédé
de préparation du composé de formule :
FN
`NI-(N-..>"--CH2 dans lequel on fait réagir et F-S-N
BREVE DESCRIPTION DES FIGURES The present disclosure also relates to a method of for preparing the compound of formula:
FN
`NI (N - ..>" - CH2 in which one makes react and FSN
BRIEF DESCRIPTION OF THE FIGURES
[0025] FIG. 1 (ART ANTÉRIEUR) représente une voltamétrie cyclique du graphite naturel dans divers électrolytes de liquides ioniques entre 0 et 1.2 V à un rythme de balayage de 0.1 mVs-1: (a) 0.8 M
LiTFSI/EMI-TFSI; (b) 0.8 M LiTFSI/EMI-FSI; (c) 0.8 M LiTFSI/P13-FSI.
DESCRIPTION DÉTAILLÉE DE LA DIVULGATION FIG. 1 (PRIOR ART) represents a voltammetry cyclic natural graphite in various electrolytes of ionic liquids between 0 and 1.2 V at a scanning rate of 0.1 mVs-1: (a) 0.8 M
LiTFSI / EMI-TFSI; (b) 0.8 M LiTFSI / EMI-FSI; (c) 0.8 M LiTFSI / P13-FSI.
DETAILED DESCRIPTION OF THE DISCLOSURE
[0026] Les exemples qui suivent sont mentionnés à titre non-limitatif. The following examples are mentioned as non-selective limiting.
[0027] Par exemple, le composé comprenant un groupe fluorosulfonyle peut être choisi parmi :
Li+
II
II
F-S-N-S-F
II II
LiII +
F-S-N _____________________ II
=
0 Li+
Il -F¨S¨C
o Li+ 0 F
m- 011 F¨SII II
Ne , H2 et NS//. For example, the compound comprising a group fluorosulfonyl can be chosen from:
Li +
II
II
FSNSF
II II
LiII +
FSN _____________________ II
=
0 Li +
He -FSC
o Li + 0 F
m- 011 FISHI II
Born , H2 and NS //.
[0028] Par exemple, lors du procédé de préparation du composé
de formule :
IIo F-S-N
I I
dans lequel on fait réagir S02F2 avec l'imidazole, en présence d'une base forte, la base forte peut être par exemple une base choisie parmi HMDS, LiHMDS, (tBu)3N, triéthylamine, methyllithium, buthyllithium, LDA, LDEA, LiCO3, pempidine, et les bases phosphazene bases (P1-t-Bu, P2-Et, P2-F).
Synthèse de Précurseur ¨ nouveau réactif permettant d'introduire un groupement SF02-For example, during the process for preparing the compound of formula:
Ilo FSN
II
wherein SO 2 F 2 is reacted with imidazole in the presence of a strong base, the strong base may be for example a base selected from HMDS, LiHMDS, (tBu) 3N, triethylamine, methyllithium, butyllithium, LDA, LDEA, LiCO3, pempidine, and bases phosphazene bases (P1-t-Bu, P2-Et, P2-F).
Synthesis of Precursor - new reagent for introducing a group SF02-
[0029] Le N-Fluorsulfonimide imidazole (2), NFSI, peut être préparé à partir du Sulfuryl Fluoride (1) commercialisé presque exclusivement en Amérique du nord par la compagnie Dow Chemical sous le nom commercial VikaneTM. N-Fluorsulfonimide imidazole (2), NFSI, may be prepared from Sulfuryl Fluoride (1) marketed almost exclusively in North America by Dow Chemical under the trade name VikaneTM.
[0030] Le proceed implique une réaction de l'imidazole avec le Fluorure de Sulfuryl, en présence d'une base forte pour préparer le précurseur (2) NFSI selon le schéma suivant :
Schéma 1:
IIIl F S F ______________________ F¨S¨N
II II
(1) (2) .. The process involves a reaction of imidazole with the Sulfuryl fluoride, in the presence of a strong base to prepare the precursor (2) NFSI according to the following scheme:
Figure 1:
IIThere FSF ______________________ F¨S¨N
II II
(1) (2) ..
[0031] Le NFSI est purifié par une simple distillation et pourra par la suite être utilisé en tant que précurseur sans chlore, bon marché et facile à manipuler.
Synthèse de l'anion FSI The NFSI is purified by a simple distillation and may by subsequently be used as a precursor without chlorine, cheap and easy to manipulate.
Synthesis of the FSI Anion
[0032] La réaction de NFSI avec un demi-équivalent de LiNI-suivi d'une acidification du milieu réactionnel, donnerait en synthèse direct le LiFSI convoité exempt de chlore et de potassium Schéma 2:
0 0 Li 0 H7'''.N 1/2 LiNH2 II - II
F¨S¨N 7.- F S N S F
I I \-:.---- H H
o o 0 (2) (3) Synthèse des anions stabilisés avec un ou deux groupement nitrile A. Synthèse de l'anion FSO2NCN (4) The NFSI reaction with a half-equivalent of LiNI-followed by an acidification of the reaction medium, would give in synthesis direct the coveted LiFSI free of chlorine and potassium Figure 2:
0 0 Li 0 H7 '''N 1/2 LiNH2 II - II
F¨S¨N 7.- FSNSF
II \ -: .---- HH
oo 0 (2) (3) Synthesis of stabilized anions with one or two nitrile groups A. Synthesis of FSO2NCN Anion (4)
[0033] Également, la réaction de Cyanamide avec le NFSI 2 par une réaction d'addition-élimination. La délocalisation de la charge négative sur la molécule ainsi obtenue, grâce au groupement CN et FS02 lui donnerait une stabilité électrochimique accrue et améliorait ainsi la stabilité des batteries aves un atome de Fluor de moins (plus écologique).
Schéma 3:
+
0 0 Li Il 7*-----N H2N ___________________________ ¨N H _ F¨S¨N ______________________________________ - F S N--- _¨_N
H\__-!--- H
o 0 (2) (4) B. Synthèse de l'anion FSO2CH(CN)2 Also, the reaction of Cyanamide with NFSI 2 by an addition-elimination reaction. Offshoring of the load negative on the molecule thus obtained, thanks to the CN group and FS02 would give it increased electrochemical stability and improve thus the stability of the batteries has a fluorine atom of less (more ecological).
Figure 3:
+
0 0 Li He 7 * ----- N H2N ___________________________ ¨NH _ F¨S¨N ______________________________________ - FS N --- _¨_N
H \ __-! --- H
o 0 (2) (4) B. Synthesis of FSO2CH anion (CN) 2
[0034] Une autre possibilité serait de faire réagir le NFSI avec le Malonitrile. Ceci permet, dans un souci écoresponsable, d'avoir un anion aussi performant que le FSI mais avec moins de Fluor. Toujours dans le but d'obtenir une grande délocalisation de la charge négative qui donne une stabilité chimique et électrochimique accrue à l'anion.
Schéma 4:
N
0 0 +
I l /-------N CH2(CN)2 Il Li _ F¨S¨N ______________________________________ Io- F¨S¨C
Il-\,--% Il \N
C. Synthèse de l'anion FSO2NSO2CF3 Another possibility would be to react the NFSI with the Malononitrile. This allows, in an eco-responsible way, to have an anion as efficient as the FSI but with less Fluor. Still in the purpose of getting a large delocalization of the negative charge which gives increased chemical and electrochemical stability to the anion.
Figure 4:
NOT
0 0 +
I l / ------- N CH2 (CN) 2 Il Li _ F¨S¨N ______________________________________ I- F¨S¨C
He - \, -% He \NOT
C. Synthesis of FSO2NSO2CF3 Anion
[0035] De plus, le précurseur 2 permettrait de mettre en évidence une nouvelle voie de synthèse rapide et efficace et sans Chlore (corrosive pour les piles) du sel N-(fluorosulfuryl)sulfonamide de Lithium 6 à partir de trifluorométhanesulfonamide (Aldrich).
Schéma 5:
0 (") Li+ 0 F
Il 7.---N CF3SO2NH2 H - II
F¨S¨N 7.F S N S ________ F
I I\-_-!-- Il Il Synthèse de nouveaux monomères In addition, the precursor 2 would make it possible to highlight a new fast and efficient synthesis route without chlorine (corrosive for batteries) Lithium N- (fluorosulfuryl) sulfonamide salt 6 from trifluoromethanesulfonamide (Aldrich).
Figure 5:
0 (") Li + 0 F
He 7 .--- N CF3SO2NH2 H - II
F¨S¨N 7.FSNS ________ F
II \ -_-! - He He Synthesis of new monomers
[0036] L'attaque nucléophile de réactif de Grignard sur le produit 2 donnerait le monomère 7.
Schéma 6:
Mg+Br 0 FN //c H /N
F¨S¨N The nucleophilic attack of Grignard reagent on the product 2 would give the monomer 7.
Figure 6:
Mg + Br 0 FN // c H / N
FSN
[0037] Également, l'allylamine peut réagir avec le 2 en milieu basique pour donner le monomère 8 selon le schéma suivant Schéma 7:
F¨S¨N
I 0 "
Synthèse de nouveaux polymères électrolytes à partir des monomères 7 et 8. Also, the allylamine can react with the 2 in the middle basic to give the monomer 8 according to the following scheme Figure 7:
FSN
I 0 "
Synthesis of new electrolyte polymers from monomers 7 and 8.
[0038] Il est possible de préparer les polymères suivants (voir les schéma 8 et 9) :
Schéma 8:
F -S Polymérisation H3C CH3 // N...----"NCH2 ________________ . 0 ,,-,, -n 0 base \\ 1/4,1-1 ,s +
F- \\ Li Schéma 9:
S -// NNH
õ.--CH2 Polymérisation base \\ ,,N1 n S
+
Li F
\O It is possible to prepare the following polymers (see diagram 8 and 9):
Figure 8:
F -S H3C CH3 polymerization // N ... ---- "NCH2 ________________. 0 ,, -,, -not 0 basis \\ 1 / 4,1-1 , s +
F- \\ Li Figure 9:
S -// NNH
õ .-- CH2 Polymerization base \\ ,, N1 n S
+
Li F
\ O
[0039] Le marché global des batteries au Lithium pour les applications en véhicules est estimé à 221 Milliards de $ US d'ici 2024. The global market for lithium batteries for Vehicle applications are estimated at US $ 221 billion by 2024.
[0040] Les électrolytes des piles au lithium continuent à prouver des problèmes de stabilités, puretés, sécurités et de coûts élevés. The electrolytes of lithium batteries continue to prove problems of stability, purity, safety and high costs.
[0041] La technologie décrite dans la présente demande propose une nouvelle voie de synthèse, sans chlore, de nouveaux polymères électrolytes pour les piles au lithium ayant des anions fluorés chimiquement et électro-chimiquement très stables et à faibles poids moléculaires. Cette voie de synthèse ne passe pas par des précurseurs chlorés. Ceci est très important pour simplifier les étapes de synthèse et les purifications subséquentes. The technology described in this application proposes a new way of synthesis, without chlorine, of new polymers electrolytes for lithium batteries having fluorinated anions chemically and electro-chemically very stable and low weight molecular. This synthetic route does not go through precursors chlorinated. This is very important to simplify the synthesis steps and subsequent purifications.
[0042] Les électrolytes ainsi obtenus peuvent être exempts de toutes traces de Chlores. Ce dernier étant très corrosif pour les batteries au Lithium. The electrolytes thus obtained may be free of all traces of chlorines. The latter being very corrosive for batteries Lithium.
[0043] Il est à noter que, une telle voie de synthèse économique et sans chlore de LiFSI 3 est très recherchée depuis des années. Par conséquent, une cette voie trouvera un marché important à très court terme et des retombés économiques importantes. It should be noted that such an economic synthesis route and without chlorine from LiFSI 3 has been in great demand for years. By therefore, one this way will find a large market in very short term and significant economic benefits.
[0044] Par ailleurs, le NFSI 1 sera un nouveau précurseur qui trouvera des applications en tant que:
= Solvant auxiliaire pour les batteries au Lithium de type carbonate = Réactif permettant d'insérer facilement la fonction FS02- dans une molécule cible biologiquement actifs. (e.g. remplacement bioisotérique). Moreover, the NFSI 1 will be a new precursor which will find applications as:
= Auxiliary solvent for carbonate type Lithium batteries = Reagent for easily inserting the FS02- function into a biologically active target molecule. (eg replacement bioisotérique).
[0045] La présente divulgation été décrite ci-dessus en référence à un mode préféré de réalisation de l'invention. Bien entendu, la réalisation qui vient d'être décrite est uniquement illustrative et elle n'est en aucun cas limitative, diverses modifications peuvent être apportées aux différents objets qui la constitue sans sortir du cadre de la présente invention. The present disclosure has been described above with reference to a preferred embodiment of the invention. Of course, the The realization just described is illustrative only and is not in no way limiting, various modifications may be made to the different objects that constitute it without departing from the scope of this invention.
Claims (12)
2. Use of the compound of claim 1 in the preparation of a compound comprising a fluorosulfonyl group:
comprenant un groupe fluorosulfonyle est choisi parmi :
et The use according to claim 2, wherein the compound comprising a fluorosulfonyl group is chosen from:
and
dans lequel on fait réagir SO2F2 avec l'imidazole, en présence d'une base forte. 5. Process for preparing the compound of formula:
in which SO2F2 is reacted with imidazole, in the presence of a base strong.
dans lequel on fait réagir LiNH2 avec 7. Process for preparing the compound of formula:
in which LiNH2 is reacted with
dans lequel on fait réagir et 8. Process for preparing the compound of formula:
in which one makes react and
dans lequel on fait réagir et 9. Process for preparing the compound of formula:
in which one makes react and
dans lequel on fait réagir et 10. Process for preparing the compound of formula:
in which one makes react and
dans lequel on fait réagir Mg+Br F12.#
et 11. Process for preparing the compound of formula:
in which one makes react Mg + Br F12. #
and
dans lequel on fait réagir et 12. Process for preparing the compound of formula:
in which one makes react and
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2959745A CA2959745A1 (en) | 2017-02-28 | 2017-02-28 | Preparation process for compounds including a fluorosulfonyl group, and new reactants allowing such chemical reactions |
| PCT/CA2018/050224 WO2018157240A1 (en) | 2017-02-28 | 2018-02-27 | Method for preparing compounds comprising a fluorosulfonyl group, and novel reagents enabling such chemical reactions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2959745A CA2959745A1 (en) | 2017-02-28 | 2017-02-28 | Preparation process for compounds including a fluorosulfonyl group, and new reactants allowing such chemical reactions |
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| CA2959745A1 true CA2959745A1 (en) | 2018-08-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CA2959745A Abandoned CA2959745A1 (en) | 2017-02-28 | 2017-02-28 | Preparation process for compounds including a fluorosulfonyl group, and new reactants allowing such chemical reactions |
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| Country | Link |
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| CA (1) | CA2959745A1 (en) |
| WO (1) | WO2018157240A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3715342A4 (en) * | 2017-11-22 | 2021-07-07 | Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences | Fluorosulfonyl-containing compound, intermediate thereof, preparation method therefor and use thereof |
| US10967295B2 (en) | 2018-11-16 | 2021-04-06 | Ses Holdings Pte. Ltd. | Processes for removing reactive solvent from lithium bis(fluorosulfonyl)imide (LiFSI) using organic solvents that are stable toward anodes in lithium-ion and lithium-metal batteries |
| US10926190B2 (en) | 2018-11-16 | 2021-02-23 | Ses Holdings Pte. Ltd. | Purified lithium bis(fluorosulfonyl)imide (LiFSI) products, methods of purifying crude LiFSI, and uses of purified LiFSI products |
| US10734664B1 (en) | 2019-03-01 | 2020-08-04 | Ses Holdings Pte. Ltd. | Purified hydrogen bis(fluorosulfonyl)imide (HFSI) products, methods of purifying crude HFSI, and uses of purified HFSI products |
| US11014945B2 (en) | 2019-04-06 | 2021-05-25 | Trinapco, Inc. | Sulfonyldiazoles and N-(fluorosulfonyl)azoles, and methods of making the same |
| US11542236B2 (en) | 2019-04-06 | 2023-01-03 | Trinapco, Inc. | Sulfonyldiazoles and N-(fluorosulfonyl)azoles, and methods of making the same |
| JP2022510124A (en) | 2019-08-22 | 2022-01-26 | フジアン ヨンジン テクノロジー カンパニー リミテッド | A new synthetic process for fluorinated conductive salts for lithium-ion batteries |
| CN111620315A (en) * | 2020-07-22 | 2020-09-04 | 上海华谊（集团）公司 | Preparation method of lithium bis (fluorosulfonyl) imide |
| CN111816920B (en) * | 2020-08-31 | 2021-06-29 | 珠海冠宇电池股份有限公司 | Electrolyte solution and battery |
| CN113972398B (en) * | 2021-10-18 | 2022-08-16 | 傲普(上海)新能源有限公司 | Nonaqueous electrolyte and nonaqueous electrolyte battery using same |
-
2017
- 2017-02-28 CA CA2959745A patent/CA2959745A1/en not_active Abandoned
-
2018
- 2018-02-27 WO PCT/CA2018/050224 patent/WO2018157240A1/en active Application Filing
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