Process for the synthesis of salts comprising an organic anion useful as ionic conducting materials

Abstract

Title: Process for the synthesis of salts comprising an organic anion useful as ionic conductive materials The present invention relates to a process for the preparation of a salt comprising an organic anion corresponding to a formula (I) comprising: M+, an alkali metal cation; R1, R2, R3, R4, independently, a radical chosen from: chlorine, anionic sulfonamide units of formula (IIa): Ra-SO2-N--, and anionic dinitrile units of formula (IIIa): CN-(Rb)—CN, with at least one of the radicals R1, R2, R3, R4 being other than chlorine; said process comprising at least the step of contacting, in a solvent medium and in the presence of an alkali metal base, chloranil with at least one compound of formula (II) Ra-SO2-NH2 or (III) CN-Rb-CN to form said salt comprising an organic anion of formula (I).

Description

Title of the invention: Process for the synthesis of salts comprising an organic union useful as ionic conductive materials Technical field

[0001] The present invention relates to salts comprising an organic anion, in particular useful as ionic conductive materials, in particular in electrolytes for batteries and aims in particular to propose a new route for the synthesis of these salts. Prior art

[0002] Today, lithium batteries dominate sectors in which energy autonomy is a primary criterion, such as the transport sectors, in particular electric or hybrid transport, and in particular individual vehicles, IT, mobile telephony, or microelectronics. Given this wide variety of uses, the expectations of lithium-ion batteries in terms of safety, performance (improved ionic conductivity, electrochemical stability and the lithium ion transport number of electrolytes for lithium batteries), and cost are increasingly demanding.

[0003] The invention is more particularly relevant to the development of new generations of batteries for the electrification of transport, in particular individual vehicles. Largely dominated by lithium-ion technology, electric transport must consider new technologies to address various technological obstacles. The electrolytes used in lithium batteries are most often liquid, and are obtained by dissolving a highly conductive salt in a solvent or a mixture of solvents, generally non-aqueous. However, these electrolytes can be subject to thermal runaways, and to short circuits due to the appearance of uncontrolled dendritic growth of lithium, an undesirable phenomenon likely to be observed during battery charging.

[0004] To overcome this risk of thermal runaway, which is particularly undesirable for use in vehicles, solid polymer electrolytes prepared by dissolving a highly conductive salt in a polymer appear to be particularly advantageous. Document EP 0 850 921 A1 describes in particular conductive salts suitable for this use. These are ionic compounds derived from malononitrile in which the anionic charge is delocalized. However, the syntheses of the compounds proposed in document EP 0 850 921 are in particular syntheses requiring several successive steps. What is more, a certain number of the precursors used during these syntheses are relatively expensive and / or toxic. However, In addition to the desire to increase performance and safety, there are also environmental challenges, which are pushing manufacturers to turn to batteries with a lower environmental impact, in order to free themselves from the use of critical resources.

[0005] There therefore remains a need to have electrolytes, particularly for lithium batteries, with satisfactory electrochemical stability, high ionic conductivity and a high lithium ion transport number.

[0006] It would further be advantageous for such an electrolyte, comprising as conductive material salts comprising an organic anion of alkali metals, to have a reduced mass, conducive to obtaining a battery having an increased energy density, and therefore an increased potential autonomy.

[0007] There also remains a need for these electrolytes to take advantage of salts comprising an organic anion of alkali metals which are easy, simplified and inexpensive to synthesize.

[0008] There also remains a need for these salts comprising an organic anion of alkali metals for electrolytes and their methods of synthesis to be environmentally friendly.

[0009] The present invention aims precisely to meet these requirements. Summary of the invention

[0010] Thus, the invention relates, according to a first of its aspects, to a process for the preparation of a salt comprising an organic anion corresponding to the following formula (I):

[0011] [Chem.l] in which: • M denotes an alkali metal, and preferably Li, Na or K; • n represents the associated Flag charge and has a value of 1 or 2; • q and r independently denote 1 or 2, with the value of q being adjusted to neutralize the negative charge of the compound of formula (I); • R1, R2, R3, R4 independently denote a radical chosen from: - a chlorine atom, - anionic sulfonamide units of formula (IIa): R“-SO2-N - (Ha) in which Ra denotes an aliphatic chain, linear or branched, saturated or unsaturated, comprising from 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, said chain being optionally substituted by one or more fluorine atoms, and - anionic dinitrile units of formula (Ilia): [Chem 2]

[0012] [Chem.2] CN-(R b )'-CN I * (Ilia) in which * denotes the position of the covalent bond with the cycle and Rb denotes a trivalent, linear or branched, saturated or unsaturated hydrocarbon unit, comprising from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 carbon atom; with at least one of the radicals R1, R2, R3, R4 being other than chlorine and said process comprising at least the step of bringing into contact, in a solvent medium and in the presence of an alkali metal base, 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione (or chloranil) with: (i) at least one compound of formula (II): Ra-SO2-NH2 (II), with Ra being as defined in formula (IIa), or ii) at least one compound of formula (III): CN-Rb-CN (III), with Rb being as defined in formula (IIIa) to form said salt comprising an organic anion of formula (I).

[0013] As is apparent from the examples which follow, the inventors have found that it is possible to obtain salts comprising an organic anion of formula (I) according to a very simplified process since it only requires a single reaction step consisting of reacting at least one compound of formula (II) or (III) with chloranil and having, in addition, the advantage of considering, as raw materials, commercially available products which are inexpensive and have a very reduced impact on the environment.

[0014] According to a particular embodiment, the salt comprising an organic anion of formula (I) as described previously comprises a single radical R1, R2, R3 or R4 other than a chlorine atom.

[0015] According to a particular embodiment, the salt comprising an organic anion of formula (I) as described previously comprises two radicals R1, R2, R3, R4, preferably identical, different from one chlorine atom.

[0016] According to one embodiment, the nucleophilic substitution of at least one compound of formula (II) or (III) on chloranil is carried out in the presence of an alkali metal base chosen from alkali metal hydroxides and alkali metal hydrides.

[0017] According to another of its aspects, the present invention relates to the use of a salt comprising an organic anion of formula (I) obtained according to the process of the invention as an electrolyte.

[0018] According to another of its aspects, the present invention relates to an electrolyte, in particular for electrochemical systems, formed in whole or in part from at least one salt comprising an organic anion of formula (I) obtained according to the process of the invention.

[0019] Other characteristics, variants and advantages of the processes, molecules and electrolytes according to the invention, of their preparation and of their implementation will emerge more clearly on reading the description and the examples which follow, given for illustrative and non-limiting purposes of the invention.

[0020] In the remainder of the text, the expressions “between “... and ...”, “ranging from ... to ...” and “varying from ... to ...” are equivalent and are intended to mean that the limits are included, unless otherwise stated.

[0021] Unless otherwise indicated, the expression “comprising / comprising a(n)” must be understood as “comprising / comprising at least one(n)”. Detailed description of the invention

[0022] METHOD OF THE INVENTION

[0023] As specified above, the process according to the invention is characterized by the step of bringing into contact, in a solvent medium and in the presence of an alkali metal base, 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione (or chloranil) with: i) at least one compound of formula (II): Ra-SO2-NH2 (II), with Ra denoting an aliphatic chain, linear or branched, saturated or unsaturated, comprising from 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, said chain being optionally substituted by one or more fluorine atoms, or ii) at least one compound of formula (III): CN-Rb-CN (III), with Rb denoting a trivalent, linear or branched, saturated or unsaturated hydrocarbon unit, comprising from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 carbon atom.

[0024] Advantageously, the process of the invention is representative of a so-called one-pot synthesis of the reaction product, i.e. requiring a single synthesis step from the chloranil compound, as starting product, to form the salt comprising an organic anion of formula (I) expected. The chloranil is brought into contact with at least one compound of formula (II) or (III), under the conditions according to the invention to form the salt comprising an organic anion of formula (I). The The process according to the invention does not require an additional step such as isolation or even purification of an intermediate compound between the starting product, which is chloranil, and the salt comprising a final organic anion of formula (I). The reaction takes place in a single reaction mixture. Of course, and as detailed below, the salt comprising an organic anion of formula (I) thus formed can be subject to consecutive reaction operations in order to isolate it from its synthesis medium or even to purify it.

[0025] It can be considered that the reaction of chloranil with the compound of formula (II) or (III) involves one or more aromatic nucleophilic substitutions depending on the number of units of formula (IIa) or (IIIa) expected at the level of the anionic unit forming the salt comprising an organic anion of formula (I).

[0026] The amount of chloranil reagent can vary from 0.1 to 15% by weight, preferably from 0.5 to 12% by weight, more preferably from 1 to 10% by weight, better still from 2 to 8% by weight, relative to the total weight of the reaction medium.

[0027] The quantity of compound(s) of formula (II) or (III) may vary from 0.1 to 15% by weight, preferably from 0.15 to 12% by weight, more preferably from 0.25 to 10% by weight, better still from 0.5 to 5% by weight, relative to the total weight of the reaction medium.

[0028] It is understood that the quantity of compound of formula (II) or (III) is adjusted with regard to the level of nucleophilic substitution desired on the chloranil. This adjustment falls within the skills of a person skilled in the art. For a monosubstitution, an equimolar mixture of chloranil and the compound of formula (II) or (III) chosen will be preferred. For a disubstitution, a mixture in which the compound of formula (II) or (III) is at least 2 equivalents per 1 equivalent of chloranil will be preferred.

[0029] According to a first embodiment, the method according to the invention brings chloranil into contact with at least one compound of formula (II) Ra-SO2-NH2, with Ra as described previously.

[0030] The compounds of formula (II) Ra-SO2-NH2, with Ra as described above, are in particular chosen from (Ci-Cio)alkylsulfonamides, and preferably (C1-C5)alkylsulfonamides, trifluoro(Ci-Ci0)alkylsulfonamides and preferably trifluoro(Ci-C5)alkylsulfonamides, perfluoro(C2-Ci0)alkylsulfonamides, and preferably perfluoro(C2-C5)alkylsulfonamides and mixtures thereof, more preferably it is trifluoromethanesulfonamide.

[0031] According to a second embodiment, the method according to the invention brings chloranil into contact with at least one compound of formula (III) CN-Rb-CN, with Rb as described previously.

[0032] The compounds of formula (III) CN-Rb-CN, with Rb as described above, are in particular chosen from linear or branched, saturated or unsaturated (C3-Cio)alkyldinitriles, and their mixtures and in particular from propanedinitrile (or malo- nonitrile), butanedinitrile (or succinonitrile), pentanedinitrile (or glutaronitrile), hexanedinitrile (or adiponitrile), heptanedinitrile (or pimelonitrile), roctanedinitrile (or suberonitrile), nonanedinitrile (or azelanitrile), decanedinitrile (or seba-conitrile), and mixtures thereof, more preferably being malononitrile.

[0033] The order of contacting chloranil with at least one compound of formula (II) or (III) may vary. Thus, the compound of formula (II) or (III) may be added to a suspension or solution of chloranil, or the chloranil may be added to a suspension or solution of compound (II) or (III). Preferably, the compound of formula (II) or (III), in particular combined with a base as detailed below, is added to a suspension or solution of chloranil.

[0034] As specified above, the reaction according to the invention is carried out in the presence of an alkali metal base determining the nature of the cation M in formula (I).

[0035] This alkali metal base is preferably an alkali metal hydroxide or an alkali metal hydride.

[0036] As alkali metal hydroxides, mention may be made of lithium hydroxide LiOH, sodium hydroxide NaOH, potassium hydroxide KOH, hydrated or not, and their mixtures.

[0037] As alkali metal hydrides, mention may be made of lithium hydride LiH, sodium hydride NaH, potassium hydride KH, and mixtures thereof.

[0038] The amount of alkali metal base is adjusted so that at least 2 equivalents of base, or even more, are used for 1 equivalent of compound of formula (II) or (III).

[0039] Preferably, the alkali metal hydroxide or the alkali metal hydride alone or in the presence of a compound of formula (II) or (III) is added to the reaction medium comprising the chloranil reagent. The alkali metal hydroxide or the alkali metal hydride may be added to the reaction medium in a single step or in several steps during the synthesis.

[0040] According to an alternative embodiment, the process uses chloranil with trifluoromethanesulfonamide as compound of formula (II) as described previously, and in the presence of lithium hydride.

[0041] According to an alternative embodiment, the process uses chloranil with malononitrile as compound of formula (III), and in the presence of an alkali metal hydroxide.

[0042] As specified above, the contacting step in the process is carried out in a solvent medium. The choice of this solvent medium clearly falls within the skills of a person skilled in the art.

[0043] Examples of solvent media suitable for the invention include volatile solvents, such as acetone, acetonitrile, tetrahydrofuran (THF), in particular anhydrous THF, and mixtures thereof.

[0044] By volatile solvent is meant a solvent having a saturated vapor pressure at 20°C greater than or equal to 3 kPa.

[0045] Mention may also be made of non-volatile solvents, such as water or a hydroalcoholic mixture, for example an ethanol-water mixture, or isopropanol-water.

[0046] Preferably the solvent medium is chosen from acetonitrile, tetrahydrofuran (THF), in particular anhydrous THF, and their mixtures.

[0047] Preferably, the reaction medium is maintained, under standard pressure conditions, at a temperature ranging from -5°C to 100°C, more particularly from -5°C to 90°C, better still from 0°C to 85°C, it being understood that the temperature can be maintained at a certain temperature at the start of the reaction, then be increased. According to a particular embodiment, the temperature is maintained at 0°C at the start of the reaction and then is allowed to return to room temperature, in particular to approximately 25°C.

[0048] The duration of the reaction depends on the chemical nature of the compound of formula (II) or (III) involved, and varies between 5h and 35h, preferably between 10h and 30h, more preferably between 15h and 30h. Throughout the duration of the reaction, the reaction medium is advantageously kept stirring.

[0049] According to the process of the invention, at the end of the reaction a mixture is obtained containing the salt comprising an organic anion of formula (I) expected, generally in solution or in suspension in the reaction medium.

[0050] The process according to the invention advantageously comprises a purification step following the reaction making it possible to recover the reaction product free from impurity(ies).

[0051] This purification step may include a step of filtration of the reaction medium. Depending on the solubility of the reaction product, the residue from the filtration or the filtrate obtained after filtration may be recovered.

[0052] The purification step may also comprise a step of adding a solvent to the reaction medium or to the residue or filtrate obtained during a previous filtration step. Examples of useful solvents that may be mentioned, in anhydrous or non-anhydrous form, are THF, dichloromethane (DCM), acetonitrile, acetone, methanol, and mixtures thereof. The solvent may be added in anhydrous form in order to limit the introduction of water into the reaction medium or the filtrate obtained. During this step, the solvent is added until a clear reaction medium or filtrate is obtained, which may then be concentrated, in particular concentrated using a rotary evaporator or by being placed under vacuum.

[0053] The purification step may comprise a drying step, i.e. drying in an oven, under reduced pressure using a rotary evaporator and / or under vacuum, or dried using one or more drying agents, such as for example phosphorus pentoxide P2O5.

[0054] All of these operating modes, as well as their reaction conditions clearly fall within the skills of the person skilled in the art.

[0055] Once the purification step is complete, the pure reaction product is obtained, which can be characterized by Fourier Transform InfraRed spectroscopy (FTIR), fluorine (19F NMR) or carbon (13C NMR) nuclear magnetic resonance spectroscopy, or electrospray ionization spectroscopy coupled with mass spectrometry (ESI-MS)•

[0056] The process thus makes it possible to prepare a salt comprising an organic anion of formula (I) as described previously.

[0057] According to a particular embodiment, the salt comprising an organic anion of formula (I) as described previously comprises a single radical R1, R2, R3 or R4 other than a chlorine atom.

[0058] According to a variant of this embodiment, the single radical R1, R2, R3, R4 other than a chlorine atom denotes an anionic unit chosen from (C1-C5)alkylsulfonamides, trifluoro(C1-C5)alkylsulfonamides, perfluoro(C2-C5)alkylsulfonamides and malononitrile.

[0059] According to another particular embodiment, the salt comprising an organic anion of formula (I) as described previously comprises two radicals R1, R2, R3, R4, preferably identical, different from one chlorine atom.

[0060] According to a variant of this embodiment, the salts comprising an organic anion correspond to the following formula (Ia):

[0061] [Chem.3] in which M, n, q and r are as defined previously and the radicals R1, R4 are identical, and preferably denote an anionic unit chosen from (C1-C5)alkylsulfonamides, trifluoro(C1-C5)alkylsulfonamides, perfluoro(C2-C5)alkylsulfonamides and malononitrile.

[0062] As representative of the salts comprising an organic anion of formula (I) and (Ia), the salts comprising an organic anion below may be particularly cited, in which M+ denotes Li+, Na+ and / or K+, and where appropriate, yi and y2 are integers ranging from 0 to 4:

[0063] [Chem.4] M CM has O NC

[0064] [Chem.5]

[0065] [Chem.6]

[0067] [Chem. 8]

[0068] The process according to the invention thus proves to be particularly advantageous for preparing the following salts comprising an organic anion: - the lithium salt of 2,3,5-trichloro-6-propanedinitrile-1,4-benzoquinone (compound A):

[0069] [Chem.9]

[0070] - the sodium salt of 2,3,5-trichloro-6-propanedinitrile-1,4-benzoquinone (compound B):

[0071] [Chem. 10] O

[0072] - the potassium salt of 2,3,5-trichloro-6-propanedinitrile-1,4-benzoquinone (compound C):

[0073] [Chem. 11]

[0074] the disodium salt of 2,5-dichloro-3,6-di(propanedinitrile)-l,4-benzoquinone (compound D):

[0075] [Chem. 12] O CN Na

[0076] and the lithium salt of the 2,3,5-trichloro-6-trifluoromethanesulfonamide-1,4-benzoquinone (compound E):

[0077] [Chem. 13]

[0078] Thus, the process according to the invention makes it possible, via a one-pot synthesis, to obtain a reaction product with a yield ranging from 60 to 75%, having a purity ranging from 93 to 97%.

[0079] USE OF THE COMPOUNDS OBTAINED ACCORDING TO THE INVENTION AS ELECTROLYTE

[0080] According to another of its aspects, the present invention relates to an electrolyte, in particular for electrochemical systems, comprising at least one salt comprising an organic anion of formula (I) as described previously, or even being formed in whole or in part from such a salt comprising an organic anion.

[0081] The salts comprising an organic anion of formula (I) as described above can be advantageously used in solution in organic solvents of carbonate type as liquid electrolytes, but also in solid electrolytes, in polymer matrices or composite solid electrolytes.

[0082] In particular, the salts comprising an organic anion of formula (I) as described above comprising two radicals R1, R2, R3, R4 different from a chlorine atom, a fortiori the salts comprising an organic anion of formula (Ia) as described above, can have multiple applications as ionic conductors in electrolytes.

[0083] These salts comprising an organic anion have a low molar mass while carrying a high total positive charge, thanks to the presence of their two counter-cations. The use of such salts comprising an organic anion makes it possible to offer electrolytes having a low weight in a complete battery. This also makes it possible to offer batteries with a maximum energy density, and therefore potential autonomy.

[0084] The electrolyte according to the invention can be implemented in an electrochemical system, for example a cation-ion battery, such as a lithium-ion, sodium-ion, or potassium-ion battery.

[0085] The salts comprising an organic anion of formula (I) according to the invention are therefore useful in order to obtain sodium-ion or potassium-ion batteries which offer an alternative to lithium-ion batteries, so as to do away with critical metals such as lithium.

[0086] The present invention also relates, according to yet another of its aspects, to an electrochemical system comprising an electrolyte according to the invention.

[0087] According to a particular embodiment, the electrolyte is implemented in a battery, in particular a lithium battery, a sodium battery, or a potassium battery.

[0088] The present invention also relates, according to another of its aspects, to the use of salts comprising an organic anion obtained according to the process of the invention as electrode materials capable of redox reaction.

[0089] The invention will now be described by means of the following examples, given for illustrative and non-limiting purposes of the invention. Examples EXAMPLE 1 Synthesis of compound A according to the invention

[0090] [Chem. 14] (Compound A)

[0091] A suspension of chloranil (1.73 g, 6.98 mmol) and malononitrile previously purified by sublimation (458 mg, 6.94 mmol) is placed under an argon atmosphere in 22 mL of THF. Lithium hydroxide monohydrate (638 mg, 15.1 mmol) is added to the suspension with a spatula over a period of 5 minutes. The solution is then stirred under argon for 16 hours. The solution is filtered through Celite® to remove excess lithium hydroxide. The filtrate is evaporated and the crude product is suspended in dichloromethane, collected and rinsed thoroughly. The product is dried under vacuum over P2O5 for 48 hours, then under higher vacuum (< 0.1 mbar) at 80°C for 48 hours. Compound A is obtained as a blue-black powder (1.33 g, yield = 68%).

[0092] The purity of the product was confirmed by FTIR, 13C NMR and ESLMS. NMR (400 MHz, THF-d8) 7Li: ô: 0.25 ppm (external reference LiBF4, ô: -2.59 ppm). 13C: ô: 176.51, 165.63, 143.93, 143.08, 136.50, 120.66, 109.61, 50.80 ppm. ESLMS(-): m / z = 272.90. [C9N2O2C13]-: Theoretical mass = 272.90. FTIR: v = 2218, 1676, 1600, 1497, 1222, 1098, 719 cm1. EXAMPLE 2 Synthesis of compound B according to the invention

[0093] [Chem. 15] (Compound B)

[0094] A suspension of chloranil (1.94 g, 7.82 mmol) and malononitrile previously purified by sublimation (517 mg, 7.83 mmol) is placed under an argon atmosphere in 25 mL of anhydrous THF. The suspension is cooled with an ice bath, then sodium hydroxide (682 mg, 16.7 mmol) is added. The solution is then stirred under argon for 20 h at room temperature. The solution is filtered through Celite®. The filtrate is evaporated and the crude product is suspended in dichloromethane, collected and rinsed thoroughly. The product is dried under vacuum over P2O5 at 50°C, then under higher vacuum (< 0.1 mbar) at 120°C overnight. Compound B is obtained in the form of a dark blue powder (2.12 g, yield = 91%).

[0095] The purity of the product was confirmed by FTIR, 13C NMR and ESLMS. 13C NMR (400 MHz, MeOD): ô: 177.32, 167.63, 144.51, 144.32, 137.51, 121.64, 110.50, 68.84 ppm. ESLMS(-): m / z = 272.91. [C9N2O2C13]-: Theoretical mass = 272.90. FTIR: v = 2200, 2186, 1678, 1575, 1489, 1217, 1093, 719, 605 cm1. EXAMPLE 3 Synthesis of compound C according to the invention

[0096] [Chem. 16] (Compound C)

[0097] A suspension of chloranil (1.96 g, 7.88 mmol) and malononitrile previously purified by sublimation (521 mg, 7.88 mmol) is placed under an argon atmosphere in 25 mL of anhydrous THF. The suspension is cooled with an ice bath, then ground potassium hydroxide (981 mg, 16.1 mmol) is added. The solution is then stirred for 17 h at room temperature. The precipitate obtained is collected and rinsed thoroughly with tetrahydrofuran then dichloromethane until a clear filtrate is obtained. Acetone is added and the solution is filtered through Celite®. The filtrate is evaporated, dried under reduced pressure over P2O5 at 50°C then under higher vacuum (< 0.1 mbar) at 120°C overnight. The product is ground under an inert atmosphere and further dried under high vacuum at 120°C for 2 days. Compound C is obtained as a dark blue powder (1.62 g, yield = 66%).

[0098] The purity of the product was confirmed by FTIR, 13C NMR and ESLMS. 13C NMR (400 MHz, DMSO-d6): ô: 175.84, 165.24, 142.27, 142.09, 135.90, 120.30, 108.01,48.90 ppm. ESLMS(-): m / z = 272.90. [C9N2O2C13]-: Theoretical mass = 272.90. FTIR: v = 2207, 2191, 1677, 1603, 1506, 1214, 1097, 721, 601 cmA EXAMPLE 4 Synthesis of compound D according to the invention

[0099] [Chem. 17] (Compound D)

[0100] To a solution of malononitrile (780 mg, 11.8 mmol) in 20 mL of acetonitrile is added ground sodium hydroxide (972 mg, 23.8 mmol). The solution is stirred for 15 minutes before being added to a suspension of chloranil (1.94 g, 5.94 mmol) in 15 mL of acetonitrile. The flask containing the malononitrile solution is rinsed several times, so that the reaction medium comprises 80 mL of acetonitrile in total. The reaction medium is heated to reflux for 28 h, then allowed to return to room temperature. The reaction medium is filtered and washed with acetonitrile and acetone. A crude product is recovered and solubilized in a 1:1 acetone / methanol mixture, and filtered through Celite®. The filtrate is evaporated and the product is suspended in tetrahydrofuran. The product is collected and rinsed thoroughly with tetrahydrofuran and then dichloromethane. The product is then dried under reduced pressure over P2O5 at 50°C and then under higher vacuum (< 0.1 mbar) at 120°C overnight. The product is ground under an inert atmosphere and further dried under high vacuum at 120°C for 2 days. Compound D is obtained in the form of a brown powder (1.32 g, yield = 64%).

[0101] The purity of the product was confirmed by FTIR, 13C NMR and ESLMS. 13C NMR (400 MHz, DMSO-d6): δ: 170.52, 145.43, 121.61, 106.19, 47.37 ppm. ESLMS(-): m / z = 302.95 [Ci2N4O2C12]-: Theoretical mass = 302.95. FTIR: v = 2212, 2185, 1588, 1498, 1292, 608 cm1. EXAMPLE 5 Synthesis of compound E according to the invention

[0102] [Chem. 18] (Compound E)

[0103] In a glove box, trifluoromethanesulfonamide (270 mg, 1.76 mmol) is solubilized in 5 mL of anhydrous tetrahydrofuran in a Schlenk tube. Lithium hydride LiH (28.0 mg, 3.52 mmol) is added using a spatula, and the solution is left to stir for 1 h 30 after the end of hydrogen degassing, leading to a white precipitate. On a Schlenk line, a suspension of chloranil (432 mg, 1.74 mmol) in 10 mL of anhydrous tetrahydrofuran is cooled with an ice bath. Using a transfer cannula, the suspension of lithiated trifluoromethanesulfonamide (the suspension having been rinsed several times with anhydrous tetrahydrofuran) is added. The reaction medium is stirred for 20 hours, allowing it to return to room temperature. The solution is filtered with filter paper on a transfer cannula. The filtrate is evaporated and then suspended in anhydrous dichloromethane. The dark purple product is washed thoroughly with anhydrous dichloromethane. The product is dried under reduced pressure over P2O5 and then under higher vacuum (< 0.1 mbar) at 120°C overnight. Compound E is obtained in the form of a dark purple powder (403 mg, yield = 64%).

[0104] NMR (400 MHz, MeOD) 7Li: ô: 1.40 ppm (external ref LiBF4: -0.39 ppm). 19F: ô: -81.57 ppm (93% purity with 7% di-substituted by-product at ô: -81.71 ppm, external ref C6F6: -165.38 ppm). 13C NMR: ô: 174.26, 173.02, 149.40, 142.26, 138.43, 122.92, 120.38 ppm. ESLMS(-): m / z = 355.87 [C7CI3F3NO4S]-: Theoretical mass = 355.86. Di-substituted product observed at m / z = 468.86. FTIR: v = 1696, 1642, 1532, 1392, 1180, 1074 cm1.

Claims

Claims

1. A process for the preparation of a salt comprising an organic anion corresponding to the following formula (I): "“(D in which: • M denotes an alkali metal, and preferably Li, Na or K; • n represents the charge of the associated anion and has a value of 1 or 2; • q and r independently denote 1 or 2, with the value of q being adjusted to neutralize the negative charge of the compound of formula (I); • R1, R2, R3, R4 independently designate a radical chosen from: - a chlorine atom, - anionic sulfonamide units of formula (IIa): R“-SO2-N - (lia) in which Ra denotes an aliphatic chain, linear or branched, saturated or unsaturated, comprising from 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, said chain being optionally substituted by one or more fluorine atoms, and - anionic dinitrile units of formula (Ilia): CN-(R b )'-CN < llhu I * in which * denotes the position of the covalent bond with the cycle and Rb denotes a trivalent, linear or branched, saturated or unsaturated hydrocarbon unit, comprising from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 carbon atom; with at least one of the radicals R1, R2, R3, R4 being other than chlorine and said process comprising at least the step of bringing into contact, in a solvent medium and in the presence of an alkali metal base, 2,3,5,6-tetrachlorocyclohexa-2,5-diene-1,4-dione or chloranil with:

2.

3.

4. (i) at least one compound of formula (II): Ra-SO2-NH2 (II), with Ra being as defined in formula (Ha), or ii) at least one compound of formula (III): CN-Rb-CN (III), with Rb being as defined in formula (IIIa) to form said salt comprising an organic anion of formula (I). A method according to claim 1, wherein the salt comprising an organic anion of formula (I) comprises a single radical R1, R2, R3 or R4 other than a chlorine atom. Process according to claim 1, in which the salt comprising an organic anion of formula (I) comprises two radicals R1, R2, R3, R4, preferably identical, different from one chlorine atom. The method of claim 3, wherein the salt comprising an organic anion corresponds to the following formula (Ia):

5.

6. in which M, n, q and r are as defined in claim 1 and the radicals R1, R4, are identical. Process according to any one of the preceding claims, in which the salt comprising an organic anion is obtained after the step of bringing chloranil into contact with at least one compound of formula (II) as defined in claim 1, in particular chosen from (CrC 10)alkylsulfonamides, and preferably (Ci-C5)alkylsulfonamides, trifluoro(Ci-Cio)alkylsulfonamides and preferably trifluoro(Ci-C5)alkylsulfonamides, perfluoro(C2-Ci0)alkylsulfonamides, and preferably perfluoro(C2-C5)alkylsulfonamides and mixtures thereof.Process according to any one of the preceding claims, in which the salt comprising an organic anion is obtained after the step of bringing chloranil into contact with at least one compound of formula (III) as defined in claim 1, in particular chosen from linear or branched, saturated or unsaturated (C3-C10)alkyldinitriles, and mixtures thereof, in particular from propanedinitrile or malononitrile, butanedinitrile, pentanedinitrile, hexanedinitrile, heptanedinitrile, octanedinitrile, nonanedinitrile, decanedinitrile, and mixtures thereof. and more preferably being malononitrile.

7. Process according to any one of the preceding claims, in which the quantity of chloranil reagent varies from 0.1 to 15% by weight, preferably from 0.5 to 12% by weight, more preferably from 1 to 10% by weight, better still from 2 to 8% by weight, relative to the total weight of the reaction medium.

8. Process according to any one of the preceding claims, in which the quantity of compound(s) of formula (II) or (III) varies from 0.1 to 15% by weight, preferably from 0.15 to 12% by weight, more preferably from 0.25 to 10% by weight, better still from 0.5 to 5% by weight, relative to the total weight of the reaction medium.

9. A method according to any one of the preceding claims, wherein said base is selected from alkali metal hydroxides, such as lithium hydroxide LiOH, sodium hydroxide NaOH, potassium hydroxide KOH, hydrated or not, and mixtures thereof, and alkali metal hydrides, such as lithium hydride LiH, sodium hydride NaH, potassium hydride KH, and mixtures thereof.

10. A method according to any one of the preceding claims, wherein the solvent medium is chosen from acetonitrile, tetrahydrofuran (THF), in particular anhydrous THF, and mixtures thereof.

11. Process according to any one of the preceding claims, in which the reaction medium is maintained at a temperature ranging from -5°C to 100°C, more particularly from -5°C to 90°C, better still from 0°C to 85°C.

12. A method according to any preceding claim, further comprising a purification step.

13. Use of a salt comprising an organic anion of formula (I) obtained according to the process described according to any one of claims 1 to 12, as electrolyte.

14. Electrolyte, in particular for electrochemical systems, formed in whole or in part from at least one salt comprising an organic anion of formula (I) obtained according to the process described according to any one of claims 1 to 12.

15. Electrochemical system comprising an electrolyte according to the preceding claim.

16. Use of salts comprising an organic anion of formula (I) obtained according to the process described according to any one of the claims- indications 1 to 12 as electrode materials capable of redox reaction.