USE OF IONIC LIQUIDS AS ADJUVANT IN ELECTROCHEMISTRY

专利摘要:
The present invention relates to the use of ionic liquids as an adjuvant in electrochemistry. More particularly, the invention relates to the use of ionic liquids to solubilize in the aqueous phase or to increase the aqueous solubility of at least one organic molecule.
公开号:FR3052598A1
申请号:FR1655373
申请日:2016-06-10
公开日:2017-12-15
发明作者:Didier Floner；Ludovic Paquin；Solene Guiheneuf；Florence Geneste；Jean-Pierre Bazureau
申请人:Centre National de la Recherche Scientifique CNRS；Universite de Rennes 1；
IPC主号:

专利说明:

The invention relates to the use of ionic liquids as an adjuvant in electrochemistry.
More particularly, the invention relates to the use of ionic liquids for solubilizing in the aqueous phase or increasing the aqueous solubility of at least one organic molecule.
A solution is a mixture of a compound in a large amount and a small amount. The compound in large quantity is called solvent and the compound in small quantity is called solute. The mixture obtained enb'e the solvent and the solute constitutes a liquid phase which remains homogeneous due to intermolecular interactions existing between the solute and the solvent. This phenomenon is defined as dissolution and is limited to a quantity of solute beyond which saturation is reached. At this stage the solute no longer dissolves and the solution becomes heterogeneous. The excess solute leads to the formation of a second phase generally of a solid nature but which can sometimes appear in the form of a liquid immiscible with the initial solution.
To optimize the solubilization of a molecule, the simplest approach is to reason according to its polarity characterized by the dipole moment, μ, whose unit is the Debeye (D). Thus, a non-polar organic molecule will be soluble in an apolar or slightly polar solvent (μ <ID) such as hexane, cyclohexane, tetrachloromethane, toluene, etc. Inversely, the dissolution of a polar molecule is favored by a polar solvent (μ> 1.5 D) such as water, dimethylsulfoxide (DMSO), acetone ...
The low solubility of a molecule in a solvent is a constraint in the case of a chemical synthesis whose purpose is to obtain a large quantity of a desired product. This limit necessarily leads to the use of a high volume of solvent which quickly becomes unmanageable. But this constraint can become insurmountable as soon as it is necessary to dissolve a molecule in a conductive solution of the current. In this context it is necessary to take into account, on the one hand, the dissolution of a conducting salt and, on the other hand, the dissolution of an organic molecule. These solutions, which could be called molecular electrolytic solutions, are particularly suitable for syntheses by electrochemistry (electrosynthesis) and electrochemical storage processes (batteries and batteries). Their realization involves two stages of dissolutions which prove to be counterproductive between them.
The first step consists in dissolving an ionic salt (eg NaCl, Na2SO4, KOH, KCL) whose objective is to release at least 0.1 mM of positive and negative charges so as to ensure an ionic conductivity. The dissolution of the salt is facilitated by a polar solvent and the capacity to dissociate the charges is measured by the value of the relative permittivity of the solvent noted: Sr. A polar solvent of high pennittivity such as water (Sr = 80) separates easily positive and negative charges. On the other hand, a low permittivity solvent such as ethanoic acid = 6.2) does not separate the charges and preferentially forms pairs of ions, which leads to a low ionic conductivity.
The second step is to dissolve the organic molecules. Unfortunately the most dissociating polar solvents such as water, propylene carbonate or formic acid are due to their characteristics of very bad solvents for solubilizing these molecules which generally comprise low polar or apolar groups such as aliphatic or aromatic groups or one or more non-ionized functions such as: -NH2; COOH; SO3H ... Finally these molecules are preferentially soluble in an apolary solvent.
In conclusion, to develop a molecular electrolytic solution, the solvent should be both polar and apolar and have a high relative permittivity. Unfortunately a solvent with these parameters does not exist. The following examples are revealed from this problem. Conventional salts such as NaCl, KCl, Na2SO4 are very soluble in polar solvents of high relative permittivity. It should be noted that, thanks to the combination of these two parameters (polarity and permittivity), water is the only solvent capable of forming a solution whose ionic conductivity makes it possible to reach currents of 1 A.cm "^ Between two electrodes immersed in this solution, water is a poor solvent for solubilizing organic molecules containing apolar groups.
Conversely, an organic solvent which is solubilized for organic molecules such as dichloromethane will not dissolve or very little a conventional ionic salt, which makes it very little conductor of the current. However, there are intermediate solvents such as DMSO which can both dissolve organic molecules and ionic salts. But, DMSO due to the weakness of its relative permittivity is a dissociative solvent that leaves few charges in solution which limits the ionic conductivity of the medium.
As a result, the increase in solubility can only be achieved, to date, by a modification of the nature of the electrolytic salt or the organic molecule. But these two transformations quickly show their limits:
Electrolytic salt: the organic molecules are preferentially soluble in organic solvents (dichloromethane, acetonitrile, etc.) and therefore the concern is to solubilize positive and negative charges in the organic medium to produce an electrolytic solution. One solution is to use molecular ions in which the positive or negative charge is protected by an apolar environment. This is for example the case of tetra-n-butylammonium hexafluorophosphate.
In fact, in the case of tetra-butylammonium, for each ion the charge is confined to the center of the molecular structure and, given the apolar environment, the surface area density is low, which leads to affinity of these ions with an organic solvent little apolar or slightly polar. This method leads to a good solubilization of the salt but to a weak dissociation of the ions. The conductivity of the solution remains low and taking into account the very high purchase price of these salts the realization of an industrial electrolytic process under these conditions seems unlikely. This technique is expressed only at the analytical stage, which uses only small volumes of solution of the order of cm.
Organic molecules: this strategy is the opposite of the previous one. It is a question of considering the solvent with which the ionic conductivity is the highest. This is the case of the water that is the best candidate because the high concentration dissolution of inorganic ionic salts (NaCl, Na2SO4, ..) does not break any problem. In addition, the pH of the solution can be controlled by using the OH - or HaO '- ions derived from the mineral compounds: NaOH, KOH, HCl, H2SO4. In this case, the solubilization of an organic molecule can not be achieved. under certain conditions: - When the molecule carries functions -OH (case of sugars) or to a lesser extent SH functions (case of certain amino acids) - When appearing in the solution the following ionizable functions: -NHa ^, - COO ", -SO3".
This strategy is satisfactory in the case of low molecular weight organic molecules where the interaction with water and the solubilizing function is strong. On the other hand, as soon as the aliphatic chains and the aromatic rings take on importance (which is the general case), it is imperative that these are accompanied by numerous ionizing functions to ensure the solubility of the molecule. Therefore, it is necessary to perform successive steps of chemical synthesis so as to functionalize the target molecule. This method is difficult and the cost increases according to the number of stages envisaged. In addition, the risk is that once the various modifications made, they cause a change in the original chemical properties of the molecule.
The solubilization of an electroactive organic molecule in a current conductive solution is therefore a major problem in the case of the implementation of electrochemical processes. This difficulty is related to the solubilization in the same solvent of a carrier electrolyte and an organic molecule whose physico-chemical properties are different. The most suitable method is to chemically modify the organic molecule or the support electrolyte so as to optimize the affinity with a suitable solvent. But this increase in solubility is based on the need to perform several chemical synthesis steps that are quickly expensive. Therefore, in an industrial context this method is inappropriate for making molecular electrolyte solutions of very large volume and high molecular concentrations. This is why one of the aims of the invention is to increase the solubility of a soluble or slightly soluble organic molecule in aqueous solution without multiplying the synthesis steps.
Another object of the invention is to solubilize an insoluble organic molecule in aqueous solution without multiplying the synthesis steps.
Another object of the invention is to provide a process for aqueous solubilization of an organic molecule.
Another object of the invention is to provide an electrolytic device for implementing an electrochemical storage method.
The present invention thus relates to the use of at least one ionic liquid to increase the solubility of at least one organic molecule in aqueous solution containing at least one inorganic salt and to obtain an electrolytic solution, wherein said at least one ionic liquid and said at least one organic molecule is present in said aqueous solution in at least substantially stoichiometric amounts.
The inventors have remarked, surprisingly, that the addition of an at least substantially stoichiometric amount of an ionic liquid to at least one soluble or slightly soluble organic molecule in aqueous solution makes it possible to increase the solubility in aqueous solution of that -this.
For the purpose of the present invention, the expression "increase the solubility of at least one organic molecule" means that in the aqueous solution in question, the organic molecule is insoluble, sparingly soluble or soluble in the absence of ionic liquid.
For insoluble organic molecules, the addition of the ionic liquid makes it possible to reach a concentration of 0.1 M of the organic molecule in aqueous solution.
For weakly soluble or soluble organic molecules, the addition of the ionic liquid makes it possible to multiply by 1.5; 2; 2.5; 3; 3.5; 4; 4.5 or even the concentration in aqueous solution of the organic molecule. This factor for increasing the solubility in aqueous solution depends on the molecular weight of the organic molecule in question.
By "aqueous solution" is meant a liquid phase mainly comprising water. This liquid phase may optionally also contain one or more additives. An additive is a compound, or mixture of compounds, added in small amounts whose role is to modify the properties of the solution. For the purposes of the invention, the term "additive" is further understood to mean anything that is not already included in the electrolytic solution of the invention, that is to say a compound or mixture of compounds, other than an ionic liquid, an organic molecule or an inorganic salt (as defined below). An additive of the invention is for example chosen from a water-soluble organic solvent (DMSO, acetonitrile, methanol, ethanol, etc.) or a mixture of a weak acid and its conjugate base so as to form a acid buffer solution or a mixture of a weak base and its conjugated acid to form a basic buffer solution. By buffer solution is meant a solution whose pH is maintained approximately unchanged despite the addition of small amounts of an acid or a base, or despite dilution. The expression "pH is kept approximately unchanged" means that a difference of less than or equal to 1 pH unit can be observed. An acid buffer solution denotes a buffer solution whose pH is between 1 and 7. A basic buffer solution designates a buffer solution whose pH is between 7 and 13. The proportion of additives in the liquid phase does not exceed 2. The term "a liquid phase comprising predominantly water" is understood to include a liquid phase composed of at least 70% water.
The term "electrolytic solulion" refers to an aqueous solution containing ions. For the purposes of the present invention, this expression defines a solution whose electrical conductivity is greater than or equal to 40 mS cm -1.
An "ionic liquid" is a salt, formed by the combination of a cation and an anion, in the liquid state at a temperature generally below 100 ° C, preferably at a temperature less than or equal to ambient temperature.
The ionic liquid of the invention is an adjuvant since it is introduced in a quantity much lower than the solvent. Its function is to modulate the solubility of organic molecules in water. The ionic liquid of the invention is therefore an adjuvant having a solubilizing role, not to be confused with a solvent because of its proportion in the electrolytic solution.
For the purposes of the present invention, the expression "in amounts at least substantially stoichiometric" means that the ratio of the molar quantities of ionic liquids and organic molecules is at least 0.8. This ratio can reach a value of 5. The upper limit of this ratio is such that it makes it possible to maintain an electrical conductivity of the electrolytic solution greater than or equal to 40 mS cm -1. In the invention, the ratio of the molar quantities of ionic liquids and organic molecules can therefore take for example the following values: 0.8; 0.9; 1; 1.5; 2; 2.5; 3; 3.5; 4; 4,5 or 5.
When the ionic liquid is introduced too much into the solution, the electrochemical response weakens sharply due to a decrease in the electrical conductivity of the solution. Indeed, beyond an ionic liquid concentration 5 times greater than the organic molecule concentration, the electrical resistance of the electrolytic solution increases very rapidly. Under these conditions, these melemugs become unsuitable for use in an electrochemical process developing strong coruants.
Conversely, for a ratio of molar quantities of ionic liquids and organic molecules of less than 0.8, the electrochemical response is improved. But, quickly the solution becomes more and more "pasty" to finish after a few minutes to freeze. The ionic liquid under these conditions is no longer able to perform its role of solubilizer.
The "electrical conductivity", expressed in S.cm "', defines the ability of a solution to let the electric charges move freely and thus allow the passage of an electric current, thus the notions of electrical conductivity and mobility At the same time, the notion of electrical conductivity is antagonistic to the notion of "electrical resistance" which reflects the property of a component to oppose the passage of an electric current.
According to one embodiment, the invention relates to the use of at least one ionic liquid to increase the solubility of at least one weakly soluble or soluble organic molecule, in aqueous solution containing at least one inorganic salt, and to obtain an electrolytic solution, wherein said at least one ionic liquid and said at least one organic molecule are present in said aqueous solution in at least substantially stoichiometric amounts.
By "increasing the solubility of at least one poorly soluble or soluble organic molecule" is meant that in the aqueous solution in question, the organic molecule is poorly soluble or soluble in the absence of ionic liquid. The addition of the ionic liquid thus makes it possible to multiply by 1.5; 2; 2.5; 3; 3.5; 4; 4.5 or even the concentration in aqueous solution of the organic molecule. This factor for increasing the solubility in aqueous solution depends on the molecular weight of the organic molecule in question.
According to one embodiment, the invention relates to the use of at least one ionic liquid to increase the solubility of at least one organic molecule in aqueous solution containing at least one inorganic salt and to obtain an electrolytic solution, wherein said at least one ionic liquid and said at least one organic molecule are present in said aqueous solution in substantially stoichiometric amounts.
The inventors have noted, in a similar way, that the addition of a substantially stoichiometric amount of an ionic liquid to at least one soluble or slightly soluble organic molecule in aqueous solution makes it possible to increase the solubility in aqueous solution thereof. .
For the purposes of the present invention, the expression "in substantially stoichiometric quantities" means that the ratio of the molar amounts of ionic liquids and organic molecules is from at least 0.8 to a value of 1.2.
Under these conditions, the electrical conductivity of the electrolytic solution is optimal.
According to one embodiment, the invention relates to the use of at least one ionic liquid for solubilizing at least one organic molecule in aqueous solution containing at least one inorganic salt and obtaining an electrolytic solution, wherein said at least one ionic liquid and said at least one organic molecule is present in said aqueous solution in at least substantially stoichiometric amounts.
The inventors have remarked, surprisingly, that the addition of an at least substantially stoichiometric amount of an ionic liquid to at least one insoluble organic molecule in aqueous solution makes it possible to solubilize the latter in aqueous solution. The expression "solubilize at least one organic molecule" refers to the aqueous solubilization of an insoluble organic molecule in aqueous solution,
In the sense of the invention, the "organic molecule insoluble in aqueous solution" is considered to mean that the organic molecule has a solubility of less than 0.1 M in aqueous solution, in the absence of ionic liquid. The addition of the ionic liqmde makes it possible to reach a concentration of 0.1 M of the organic molecule in aqueous solution.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one ionic liquid comprises a hydrophilic union.
According to an advantageous embodiment of the invention, during the reuse of at least one ionic liquid, said hydrophilic anion is chosen from methanesulphate, ethanesulphate, chloride, iodide, tetrafluoroborate, thiocyanate, dicyanamide, trifluoroacetate, nitrate or hexafluorophosphate anion. .
According to a more advantageous embodiment of the invention, when using at least one ionic liquid, said hydrophilic anion is chosen from methanesulphate, ethanesulphate, tetrafluoroborate or dicyanamide anion.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one ionic liquid comprises an aromatic heterocyclic cation. According to an advantageous embodiment of the invention, during the use of at least one ionic liquid, said at least one ionic liquid comprises an aromatic heterocyclic cation chosen from an imidazolium, a pyridinium or a quinolinium.
According to an advantageous embodiment of the invention, when using at least one ionic liquid, said at least one ionic liquid comprises a hydrophilic anion and an aromatic heterocyclic cation.
According to a preferred embodiment of the invention, when using at least one ionic liquid, said at least one ionic liquid is chosen from ethanesulfate pyridinium of formula (La), ethanesulfate imidazolium of formula ( Lb), methanesulfate imidazolium of formula (Ic), dicyanamide imidazolium of formula (1-d), tetrafluoroborate imidazolium of formula (Ie) or methanesulfate quinolinium of formula (Lf):
According to another embodiment of the invention, during reuse of at least one ionic liquid, said at least one ionic liquid comprises an aliphatic cation.
According to an advantageous embodiment of the invention, during the reuse of at least one ionic liquid, said at least one ionic liquid comprises an aliphatic cation chosen from ammonium.
According to an advantageous embodiment of the invention, when using at least one ionic liquid, said at least one ionic liquid comprises a hydrophilic anion and an aliphatic cation.
According to a preferred embodiment of the invention, when using at least one ionic liquid, said at least one ionic liquid is ammonium methanesulfate of formula (I-g):
According to one embodiment, when using at least one ionic liquid according to the invention, said at least one ionic liquid comprises a hydrophilic anion and an aliphatic cationic heterocyclic cation or an aliphatic cation; said hydrophilic anion being especially selected from methanesulfate, ethanesulfate, chloride, iodide, tetrafluoroborate, thiocyanate, dicyanamide, trifluoroacetate, nitrate or hexafluorophosphate, preferably selected from methanesulfate, ethanesulfate, tetrafluoroborate or dicyanamide; said aromatic heterocyclic cation being in particular chosen from an imidazolium, a pyridinium or a quinolinium; or said aliphatic cation being especially selected from im ammonium; said at least one ionic liquid being more preferably selected from ethanesulfate pyridinium of formula (Ia), F ethanesulfate imidazolium of formula (Ib), methanesulfate imidazolium of formula (Fc), dicyanamide imidazolium of formula (Id), tetrafluoroborate imidazolium of formula (Ie), quinolinium methanesulfate of formula (If), or ammonium methanesulfate of formula (Ig).
It is also possible to use more ionic liquids as an adjuvant, in particular according to their properties. Indeed, ionic liquid may have a high affinity with the organic molecules to be solubilized but its melting point or its viscosity are too high to obtain a solution. In this case, a second ionic liquid having more suitable properties may be added to provide a solution while increasing the solubilizing power of the adjuvant. In this case, the ionic liquid makes it possible to modulate both the solubility of the at least one organic molecule and the viscosity of the electrolytic solution.
"Viscosity" is defined as the uniform and turbulence-free flow resistance in the mass of a material. As the viscosity increases, the ability of the fluid to flow decreases, the ions possibly present in the fluid then move with a higher resistance. An increase in viscosity is therefore also related to a decrease in the electrical conductivity of a solution.
According to one embodiment of the invention, when using at least one ionic liquid, said electrolytic solution comprises two different ionic liquids.
According to an advantageous embodiment of the invention, when using at least one ionic liquid, said electrolytic solution comprises two different ionic liquids, the two ionic liquids being present in equivalent molar amount, and being together in stoichiometric amount with respect to said at least one organic molecule.
According to one embodiment, when using at least one ionic liquid according to the invention, said at least one ionic liquid is present in a volume percentage of between 5 and 20% relative to the total volume of the solution. , especially from 10 to 20%, especially by 10%,
Below 5% by volume, the ionic liquid is not introduced in sufficient quantity relative to the organic molecule to ensure its role of solubilizing adjuvant.
For a value ranging from 5% to less than 10% by volume, the addition of ionic liquid makes it possible to increase the solubility of an organic molecule in the aqueous solution without necessarily reaching the maximum solubility of the organic molecule in the aqueous solution. the water. This maximum is obtained by an addition to ionic liquid equal to 10% by volume relative to the total volume of the solution.
Thus, the solubilization of the organic molecule is obtained in a maximum manner for a stoichiometric ratio equal to 1. On the other hand, when the number of moles of ionic liquid is less than half that of the organic molecule, solubilization is no longer possible. By way of example, alizarin is soluble at a concentration of 0.1 M in an aqueous solution of 2 M KOH. With an addition of 10% of ionic liquid the concentration of alizarin in the aqueous solution of 2 M KOH increases to 0.5 M. However, 5% of ionic liquid allows to solubilize 0.25 M alizarin which corresponds to a concentration higher than the concentration of alizarin in the aqueous solution of 2 M KOH without addition of liquid ionic but a lower concentration than that obtained by the addition of 10% by volume of ionic liquid.
Beyond 20% by volume, the ionic liquid is considered as a solvent within the meaning of the invention. A percentage of ionic liquid greater than 20% by volume relative to the total volume of the solution is therefore not part of the invention.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule is polar or apolar.
The terms "polar" and "apolar" refer to the difference in electogenicity between the constituent atoms of the organic molecule. The electronegativity of an element is its tendency to attract electrons towards it.
According to an advantageous embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule is polar.
According to another advantageous embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule is apolaii-e.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule is electroactive.
For the purposes of the present invention, the term "organic electroactive molecule" the capacity of an organic molecule to be revemably oxidized eVou reduced. Reversibility is evidenced by the difference between the oxidation and reduction potential of a species. A sample of 57 mV at 25 ° C characterizes a reversible oxidation-reduction phenomenon.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule has a molecular weight of from 100 to 600 g.mol.
In this range, organic molecules called "small" and "large" are included.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule has a molecular weight of from 100 to 200 g.muF '.
An organic molecule within the meaning of the present invention whose molecular weight is between 100 and 200 g.mF * is considered a "small" organic molecule. This class of molecule generally has a solubility in a water free of ionic liquid of 0.2 to 0.5 M.
According to another embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule has a molecular weight of from 200 to 600 g.mF *.
Organic molecules having a molecular weight of from 200 to 600 g / mol are considered within the meaning of the invention as "large" molecules. Their solubility in a water free of ionic liquid is generally from 0 M to 0.2 M.
Above 600 g / mol, the organic molecule induces a too high viscosity of the aqueous solution, decreasing the conductivity of the solution below the threshold of 40 mS cm -1 defining an electrolytic solution within the meaning of the present invention. .
According to one embodiment when using at least one ionic liquid according to the invention, said at least one organic molecule has 1 to 4 fused aromatic rings, preferably 1 to 3 fused aromatic rings, more preferably 1 aromatic cycle or 3 fused aromatic rings.
Above 4 fused aromatic rings, the intermolecular interactions are too strong to allow an ionic liquid added in at least substantially stoichiometric amount to solubilize the organic molecule in aqueous solution.
According to an advantageous embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule is chosen from the family of quinones, catechols, naphthoquinones, orthonaphthoquinones or anthraquinones.
According to a more advantageous embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule is chosen from the family of quinones, catechols, naphthoquinones or orthonaphthoquinones. The organic molecules of these families belong to the category of "small" molecules within the meaning of the invention.
According to another more advantageous embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule is chosen from the family of anthraquinones.
Molecules of the anthraquinone family belong to the category of "large" molecules.
According to an advantageous embodiment, when using at least one ionic liquid according to the invention, said at least one organic molecule is hydroxylated on at least one position.
The Inventem-s have noticed that with the presence of a hydroxyl group close to one of the two carbonyl functions, that is to say in alpha or beta of one of the two carbonyl functions, the electrochemical reversibility of the molecule is assured. In addition, the presence of a hydroxyl function improves the solubility in water and particularly in basic medium.
According to an advantageous embodiment, when using at least one ionic liquid according to the invention, said at least one organic molecule is hydroxylated on at least one position and has a molecular weight of from 100 to 200 g-raoL ^
According to an advantageous embodiment, when using at least one ionic liquid according to the invention, said at least one organic molecule is hydroxylated on at least one position and has a molecular weight of from 200 to 600 g-mof .
According to a preferred embodiment of the invention, during the reuse of an ionic liquid, said at least one organic molecule is chosen from compounds of formulas (II-a) to (II-i):
According to one embodiment, when using at least one ionic liquid according to the invention, said at least one organic molecule is polar or apolar; and / or said at least one organic molecule is electroactive; and / or said at least one organic molecule has a molecular weight of from 100 to 600 g / cm 2, in particular from 100 to 200 g / ml or from 200 to 600 g / mol; and / or said at least one organic molecule has in particular 1 to 4 fused aromatic rings, preferably 1 to 3 fused aromatic rings, more preferably 1 aromatic ring or 3 fused aromatic rings; and / or said at least one organic molecule is hydroxylated on at least one position; in particular, said at least one organic molecule is chosen from the family of quinones, catechols, naphthoquinones, orthonaphthoquinones or anthraquinones, preferably chosen from compounds of formulas (II-a) to (II-i).
According to one embodiment of the invention, during the reuse of at least one ionic liquid, said at least one organic molecule has a solubility in a water free of ionic liquid of from 0 M to a value of less than 0.1 M .
The organic molecule thus defined is considered insoluble in a water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase up to 0.1 M of the solubility in a water free of ionic liquid of such an organic molecule when adding 5 equivalents of ionic liquid relative to the organic molecule.
For the purposes of the present invention, the term "solubility in water without ionic liquid" refers to the solubility of the organic molecule in an aqueous solution, as defined in the present invention, in the absence of ionic liquid.
According to another embodiment of the invention, during the use of at least one ionic liquid, said at least one organic molecule has a solubility in a water removed from ionic liquid of 0.1 M to 0.2 Mr.
The organic molecule thus defined is considered to be poorly soluble in water stripped of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase of the solubility of the poorly soluble organic molecule in a water without ionic liquid when adding a stoichiometric amount of ionic liquid with respect to the organic molecule. The addition of the ionic liquid increases the solubility of the organic molecule by 3 or 5 in the aqueous solution.
According to another embodiment of the invention, when using at least one ionic liquid, said at least one organic molecule has a solubility in a water without ionic liquid of 0.2 M to 0.5 Mr.
The organic molecule thus defined is considered to be soluble in water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase of the solubility of the soluble organic molecule in a water deprived of ionic liquid until reaching a solubility of 1M by the addition of a stoichiometric amount of ionic liquid with respect to the organic molecule.
Beyond a solubility of 0.5 M electroactive organic molecule in a water free of ionic liquid, the electrolyte solutions containing such an organic molecule can be used without adding ionic liquid in a battery.
According to one embodiment of the invention, the laws of the use of at least one ionic liquid, said at least one organic molecule has a solubility in a water free of ionic liquid from 0 M to a value less than 0, 1 M; or said at least one organic molecule has a solubility in a water free of ionic liquid of 0.1 M to 0.2 M; or said at least one organic molecule has a solubility in a water free of ionic liquid of 0.2 M to 0.5 M.
According to one embodiment, when using at least one ionic liquid according to the invention, said at least one ionic liquid and said at least one organic molecule are each present at a concentration of from 0.1 M to 1 M M, preferably from 0.1 M to 0.6 M.
Under these concentration conditions, the ionic liquid is an adjuvant within the meaning of the invention and can not be considered as a solvent.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one inorganic salt is an acidic, basic or neutral salt.
According to one embodiment of the invention, when using at least one ionic liquid, said at least one inorganic salt is a strong neutral salt selected from NaCl, KCl, Na 2 SO 4, K 2 SO 4.
According to another embodiment of the invention, during reuse of at least one ionic liquid, said at least one inorganic salt is a strong acid selected from HCl, H 2 SO 4, HClO 4. The strong acids make it possible to obtain at a high concentration, that is to say at a concentration greater than or equal to 1 M, a conductivity of the high solution, since the charges, unions and protons, are completely dissociated. In the sense of the invention, it is possible to define a conductivity as "high" if a current of 1 A flows between two electrodes of 1 cm 2 of surface distant from each other by 1 cm. This value is obtained when the charged particle in solution is the proton which is the most mobile species of all the ions (then it is OH "). At a pH of less than or equal to 1, the pH of the electrolytic solution evolves very little, without the addition of an additive. Under these conditions, only the ions ensure the electrical conductivity of the solution which is then qualified to be high.
Solutions with a pH greater than 1 and less than or equal to 7 are buffered using an additive comprising a mixture of a weak acid and its conjugate base, that is to say that the pH of the solution will evolve very little.
The mixtures between a weak acid and its conjugate base and their proportions making it possible to obtain buffer solutions whose pH is from a value greater than 1 to a value of less than or equal to 7 are known to those skilled in the art. For example, the mixture CH 3 COOH / CH 3 COO 3, Na 2 makes it possible to obtain buffer solutions whose pH is between 3.8 and 5.8. For solutions having a pH of from 1.9 to 3.9, a ClCH 2 COOH / ClCH 2 COO 3, Na 2 mixture may be chosen. The buffer solution advantageously comprises a concentration of from 0.1 to 2 M of the mixture between a weak acid and its conjugate base.
In an acidic aqueous solution buffered with the mixture CH.sub.2 COOH / CH.sub.2 CO.sub.5 N.sub.Na.sub.2, the electrical conductivity is ensured by the mobility of the predominantly present ions, that is to say CH.sub.3CO.sub.4 and Na.sub.2. larger than the proton, they move less rapidly in solution and contribute to a decrease in the electrical conductivity com- pared with a non-buffered acidic aqueous solution whose pH is less than or equal to 1.
To ensure good ionic conductivity, at least a 2M buffer solution is required, which releases 1M of positive and negative charge in solution.
Finally a conductive buffer solution is highly concentrated in various inorganic and organic ions which is a brake on the solubility of an organic molecule. In this case, the solution can be buffered for example between 0.1 and 0.5 M and the conductivity of the medium is increased by the addition of a neutral inorganic salt.
According to another embodiment of the invention, when using at least one ionic liquid, said at least one inorganic salt comprises two inorganic salts.
According to an advantageous embodiment of the invention, when using at least one ionic liquid, said two inorganic salts are chosen from a neutral inorganic salt and an acidic inorganic salt.
In particular the neutral inorganic salt is selected from NaCl, KCl, Na2SO4, K2SO4 and the acidic inorganic salt is selected from the strong acids HCl, H2SO4, HCIO4.
According to another embodiment of the invention, when using at least one ionic liquid, said at least one inorganic salt is a strong base selected from NaOH, KOH, LiOH. At a pH greater than or equal to 13, the pH of the electrolytic solution evolves very little, without the addition of an additive. Under these conditions, only the HO ions "impairs the electrical conductivity of the solution.
Solutions with a pH greater than or equal to 7 and less than 13 are buffered using an additive comprising a mixture between a weak base and its conjugated acid, that is to say that the pH of the solution will evolve very little. Mixtures between a weak base and its conjugated acid and their proportions making it possible to obtain buffer solutions whose pH is between a value of greater than or equal to 7 and less than 13 are known to those skilled in the art. The pad also helps to ensure the conductivity of the electrolyte solution. In this case, however, the electrical conductivity remains lower compared to the electrical conductivity of a non-buffered basic solution but can be increased by the addition of a basic inorganic salt. The use of at least one ionic liquid according to the invention thus involves two inorganic salts.
According to an advantageous embodiment of the invention, the laws of the use of at least one ionic liquid, said two inorganic salts are selected from a neutral inorganic salt and a basic inorganic salt.
In particular the neutral inorganic salt is selected from NaCl, KCl, Na 2 SO 4, K 2 SO 4 and the basic inorganic salt is selected from the strong bases NaOH, KOH, LiOH.
In a solution of strong acid or strong base the addition of a strong neutral salt (completely dissociated) makes it possible to increase the conductivity without increasing the quantity already important (at least 0,5 mol.L '^) in protons or hydroxides.
According to one embodiment of the invention, when using at least one ionic liquid, said inorganic salt is of concentration of from 0.5 to 3 M, more particularly from 1 M to 2.5 M, of preference 2 M.
Below 0.5 M, the amount of ions in the aqueous solution is too small to reach the conductivity of 40 mS cm -1 of the electrolytic solution of the invention.
Above 3 M inorganic salts, and according to their natm-e, several phenomena can occur since the electrolytic solutions of the invention are very charged in molecules and ions (organic molecule + ionic liquid + inorganic salts). Thus, 1) the inorganic salt can be at its solubility limit in the solution under consideration, 2) the inorganic salt can saturate the solution and its excess can cause the insolubility of the organic molecule 3) beyond the saturation Inorganic salt can reveal two liquid phases of different density.
According to one embodiment, when using at least one ionic liquid according to the invention, said at least one inorganic salt is an acidic, basic or neutral salt; in particular said at least one inorganic salt is a strong neutral salt selected from NaCl, KCl, Na2SO4, K2SO4; or said at least one inorganic salt is a strong acid selected from HCl, H 2 SO 4, HClO 4, in particular said at least one inorganic salt comprises two inorganic salts, in particular chosen from a neutral inorganic salt and an acidic inorganic salt, preferably the neutral inorganic salt is selected from NaCl, KCl, Na2SO4, K2SO4 and the acidic inorganic salt is selected from the strong acids HCl, H2SO4, HCIO4; or said at least one inorganic salt being a strong base selected from NaOH, KOH, LiOH, in particular said at least one inorganic salt comprises two inorganic salts, in particular selected from a neutral inorganic salt and a basic inorganic salt, preferably the neutral inorganic salt is selected from NaCl, KCl, Na2SO4, K2SO4 and the basic inorganic salt is selected from strong bases NaOH, KOH, LiOH; in particular said inorganic salt is of concentration of 0.5 to 3 M, more particularly of 1 M to 2.5 M, preferably 2 M.
According to one embodiment of the invention, when using at least one ionic liquid, said electrolytic solution has an electrical conductivity σ greater than 40 mS · cm -1, in particular greater than 100 mS · cm -1, preferably 100 to 200 mS.cm 'i
Below 40 mS cm -1, the conductivity becomes low as well as the intensity of the current between two electrodes. Thus, in an electrolysis process if the current is low, the transformation speed of a product is also low and the duration of the electrolysis is very long. This procedure can not be applicable to an industrial process.
Similarly for a battery or a battery if the conductivity is low the current produced is low. Conversely, the higher the conductivity, the higher the efficiency of the electrochemical process in question.
According to one embodiment of the invention, when using at least one ionic liquid, said electrolytic solution has a viscosity of 1 to 400 cP measured at 20 ° C with a shear rate of 25 s'. 1 centipoise is the viscosity of water.
According to an advantageous embodiment of the invention, when using at least one ionic liquid, said electrolytic solution has a viscosity of 1 to 125 cP measured at 20 ° C. with a shear rate of 25 seconds. ^
Since the solvent used in the present invention is water, the viscosity of the solution obtained can not be less than 1 cP. The upper limit is set at 125 cP, which corresponds to the viscosity of an electrolyte solution tested in battery mode and showing minimal performance.
According to another advantageous embodiment of the invention, when using at least one ionic liquid, said elecolytic solution has a viscosity of greater than 125 cP at a value of 400 cP, measured at 20 ° C. with a shear rate of 25%. Between a value of greater than 125 cP and a value of 400 cP, the electrolytic solution belongs to the invention if the electrical conductivity is greater than 45 mS cm -1. the solubility of the organic molecule reaches 0.5 M in aqueous solution by · adding an ionic liquid. This electrolytic solution is used in devices other than batteries, such as in electrolysis. Electrolysis is a non-spontaneous process, unlike batteries and batteries, whose energy expenditure will be higher and higher with increasing viscosity. Thus, beyond 400 cP, the energy expenditure related to the implementation of an electrolysis becomes too important for an industrial application.
According to one embodiment of the invention, when using at least one ionic liquid, said electrolytic solution has a half-wave potential of -1.1 V / ECS at -0.7 V / ECS for a basic solution whose concentration of hydroxide ions is greater than 0.5 mol.
The potential for which the current is equal to half of its limit value is called "half-wave potential" and is represented by the symbol E1 / 2. If we consider a reversible redox couple in solution (Ox / Red), the potential of the electrode is fixed at a potential called equilibrium potential (Eeq) corresponding to a current intensity equal to zero. The equilibrium potential is computable by the Nernst relationship and is therefore a function of the concentration of Ox and Red species in the solution. If a potential is applied (Eapp) to the positive direction an oxidation current appears. If the applied potential varies towards the negative direction a reduction current appears.
When the applied potential differs from the equilibrium potential and moves away from it regularly, a current appears and its intensity varies exponentially with the increase of the Eapp ~ Eeq value.
Given the phenomenon of movement of species Ox and Red in the solution quickly the intensity of the current will stabilize. In fact the intensity of the current will be proportional with the speed of arrival of these species to the electrode. Consequently, even if the applied potential continues to vary the intensity of the current remains constant (and no longer varies exponentially) and constitutes what is called a plateau (or plateau) of diffusion. The intensity of the current under this plateau is therefore the maximum value and is called the limit current (ii). In conclusion, from the equilibrium potential where the current is zero until the formation of the plateau, the curve i = f (E) is approximately close to a so-called sigmoid wave. Thus, the half-wave potential will correspond to the value of the potential applied for a current intensity equal to ii divided by 2 (ii / 2) located on the curve i = f (E).
The half wave potential is a characteristic of the Ox / Red torque.
According to one embodiment, when using at least one ionic liquid according to the invention, said electrolytic solution has an electrical conductivity σ of greater than 40 mS · cm -1, especially greater than 100 mS · cm -1, preferably from 100 to 200 mS cm -1; and / or said electrolyte solution has a viscosity of 1 to 400 cP measured at 20 ° C with a shear rate of 25 s' including 1 to 125 cP measured at 20 ° C with a shear rate of 25 s or greater than 125 cP at a value of 400 cP, measured at 20 ° C with a shear rate of 25 sec, and / or said electrolyte solution has a half-wave potential ranging from -1.1 V / ECS to -0.7 V / ECS for a basic solution whose hydroxide ion concentration is greater than 0.5 molX- ^ The invention also relates to an aqueous solubilization process of at least an organic molecule comprising a step of adding said at least one organic molecule and at least one ionic liquid in at least substantially stoichiometric amounts in an aqueous solution that may contain an inorganic salt.
According to one embodiment of the process of the invention, the step of adding said at least one organic molecule and said at least one ionic liquid in at least substantially stoichiometric amounts in said aqueous solution is followed by a solubilization step at least one inorganic salt in said aqueous solution.
According to another embodiment of the process of the invention, a step of solubilizing at least one inorganic salt in said aqueous solution is followed by the step of adding said at least one organic molecule and said at least one liquid. at least substantially stoichiometric amounts in said aqueous solution.
According to one embodiment of the process of the invention, the step of adding said at least one organic molecule and said at least one ionic liquid in at least substantially stoichiometric amounts in said aqueous solution is followed or preceded by a step solubilizing at least one inorganic salt in said aqueous solution.
According to one embodiment, in the method of the invention, said at least one ionic liquid comprises a hydrophilic anion.
According to an advantageous embodiment of the process of the invention, said hydrophilic anion is chosen from methanesulphate, ethanesulphate, chloride, iodide, tetrafluoroborate, thiocyanate, dicyanamide, trifluoroacetate, nitrate or hexafluorophosphate anion.
According to a more advantageous embodiment of the process of the invention, said hydrophilic anion is chosen from methanesulphate, ethanesulphate, tetrafluoroborate or dicyanamide anion.
According to one embodiment of the process of the invention, said at least one ionic liquid comprises an aromatic heterocyclic cation.
According to an advantageous embodiment of the process of the invention, said at least one ionic liquid comprises an aromatic heterocyclic cation chosen from an imidazolium, a pyridinium or a quinolinium.
According to an advantageous embodiment of the process of the invention, said at least one ionic liquid comprises a hydrophilic anion and an aromatic heterocyclic cation.
According to a preferred embodiment of the process of the invention, said at least one ionic liquid is chosen from ethanesulfate pyridinium of formula (Ia), ethanesulfate imidazolium of formula (Ib), methanesulfate imidazolium of formula (Ic) , the imidazolium dicyanamide of formula (Id), the imidazolium tetrafluoroborate of formula (Ie) or the quinolinium methanesulfate of formula (If):
According to another embodiment of the process of the invention, said at least one ionic liquid comprises an aliphatic cation.
According to an advantageous embodiment of the process of the invention, said at least one ionic liquid comprises an aliphatic cation chosen from ammonium.
According to an advantageous embodiment of the process of the invention, said at least one ionic liquid comprises a hydrophilic anion and an aliphatic cation.
According to a preferred embodiment of the process of the invention, said at least one ionic liquid is ammonium methanesulfate of formula (I-g):
It is also possible to use several ionic liquids as an adjuvant, in particular according to their properties. Indeed, an ionic liquid can exhibit a high affinity with the organic molecules to be solubilized but its melting point or its viscosity are too high to obtain a solution. In this case, a second ionic liquid having more suitable properties may be added to obtain a solution while increasing the solubilizing power of the adjuvant. In this case, the ionic liquid makes it possible to modulate both the solubility of the at least one organic molecule and the viscosity of the electrolysis solution. According to one embodiment of the method of the invention, said electrolytic solution comprises two different ionic liquids.
According to an advantageous embodiment of the method of the invention, said electrolyte solution comprises two different ionic liquids, the two ionic liquids being present in equivalent molar quantity, and being together in at least substantially stoichiometric amounts with respect to said at least one organic molecule.
According to one embodiment, in the method of the invention, said at least one ionic liquid is present in a volume percentage of 5 to 20% relative to the total volume of the solution, especially from 10 to 20%, particularly 10%.
Below 5% by volume, the ionic liquid is not introduced in sufficient quantity relative to the organic molecule to ensure its role of solubilizing adjuvant.
For a value ranging from 5% to less than 10% by volume, the addition of ionic liquid makes it possible to increase the solubility of an organic molecule in the aqueous solution without necessarily reaching the maximum solubility of the organic molecule in the aqueous solution. the water. This maximum is obtained by adding ionic liquid corresponding to 10% by volume relative to the total volume of the solution.
Thus, the solubilization of the organic molecule is obtained in a maximum manner for a stoichiometric ratio equal to 1. On the other hand, when the number of moles of ionic liquid is less than half that of the organic molecule, solubilization is no longer possible. . By way of example, alizarin is soluble at a concentration of 0.1 M in a 2M aqueous solution of KOH. With an addition of 10% of ionic liquid the concentration of alizarin in the aqueous solution of 2M KOH increases However, 5% of ionic liquid makes it possible to solubilize 0.25 M alizarin which corresponds to a concentration higher than the concentration of alizarin in the aqueous solution of 2 M KOH without addition of ionic liquid but a lower concentration than that obtained by the addition of 10% by volume of ionic liquid.
Above 20% by volume, the ionic liquid is considered a solvent in the sense of the invention. A percentage of ionic liquid greater than 20% by volume relative to the total volume of the solution is therefore not part of the invention.
According to one embodiment of the process of the invention, said at least one organic molecule is polar or apolar.
According to an advantageous embodiment of the process of the invention, said at least one organic molecule is polar.
According to another advantageous embodiment of the process of the invention, said at least one organic molecule is apolar.
According to one embodiment of the process of the invention, said at least one organic molecule is electroactive.
According to one embodiment of the process of the invention, said at least one organic molecule has a molecular weight of from 100 to 600 g / mol.
In this range, organic molecules called "small" and "large" are included. According to one embodiment of the process of the invention, said at least one organic molecule has a molecular weight of from 100 to 200 g / mol.
An organic molecule within the meaning of the present invention whose molecular weight is between 100 and 200 g / mol is considered a "small" organic molecule. This class of molecule generally has a solubility in a water free of ionic liquid of 0.2 to 0.5 M.
According to another embodiment of the process of the invention, said at least one organic molecule has a molecular weight of from 200 to 600 g.mu.
Organic molecules whose molecular weight is between 200 and 600 g / mol are considered in the meaning of the invention as "large" molecules. Their solubility in a water free of ionic liquid is generally from 0 M to 0.2 M.
Above 600 g / mol, the organic molecule induces a too high viscosity of the aqueous solution, decreasing the conductivity of the solution below the threshold of 40 mS cm -1 defining an electrolytic solution as defined herein. invention.
According to one embodiment of the process of the invention, said at least one organic molecule has 1 to 4 fused aromatic rings, preferably 1 to 3 fused aromatic rings, more preferably 1 aromatic ring or 3 fused aromatic rings.
Above 4 fused aromatic rings, the intermolecular interactions are too strong to allow an ionic liquid added in at least substantially stoichiometric amount to solubilize the organic molecule in aqueous solution.
According to an advantageous embodiment of the process of the invention, said at least one organic molecule is chosen from the family of quinones, catechols, naphthoquinones, orthonaphthoquinones or anthraquinones.
According to a more advantageous embodiment of the process of the invention, said at least one organic molecule is chosen from the family of quinones, catechols, naphthoquinones or orthonaphthoquinones. The organic molecules of these families belong to the category of "small" molecules within the meaning of the invention.
According to another more advantageous embodiment of the process of the invention, said at least one organic molecule is chosen from the family of anthraquinones.
The molecules of the anthraquinone family belong to the category of "large" molecules.
According to an advantageous embodiment, in the method of the invention, said at least one organic molecule is hydroxylated on at least one position.
The inventors have noted that with the presence of a hydroxyl group close to one of the two carbonyl functions, that is to say in alpha or beta of one of the two carbonyl functions, the electrochemical reversibility of the molecule is assured. In addition, the presence of a hydroxylation improves the solubility in water and particularly in basic medium.
According to an advantageous embodiment, in the method of the invention, said at least one organic molecule is hydroxylated on at least one position and has a molecular weight of between 100 and 200 g / mol.
According to an advantageous embodiment, in the process of the invention, said at least one organic molecule is hydroxylated on at least one position and has a molecular weight of between 200 and 600 g / mol.
According to a preferred embodiment of the process of the invention, said at least one organic molecule is chosen from compounds of formulas (II-a) to (II-i);
According to one embodiment of the process of the invention, said at least one organic molecule has a solubility in a water free of ionic liquid of from 0 M to a value less than 0.1 M.
The organic molecule thus defined is considered insoluble in a water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase up to 0.1 M of the solubility in a water free of ionic liquid of such an organic molecule when adding 5 equivalents of liquid ionic with respect to the organic molecule.
For the purposes of the present invention, the term "solubility in water without ionic liquid" refers to the solubility of the organic molecule in an aqueous solution, as defined in the present invention, in the absence of ionic liquid.
According to another embodiment of the process of the invention, said at least one organic molecule has a solubility in a water free of ionic liquid ranging from 0.1 M to 0.2 M.
The organic molecule thus defined is considered to be poorly soluble in a water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase of the solubility of the poorly soluble organic molecule in a water without ionic liquid when adding a stoichiometric amount of ionic liquid with respect to the organic molecule. The addition of the ionic liquid increases the solubility of the organic molecule by 3 or 5 in the aqueous solution.
According to another embodiment of the process of the invention, said at least one organic molecule has a solubility in a water without ionic liquid ranging from 0.2 M to 0.5 M.
The organic molecule thus defined is considered to be soluble in water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the Inventem's for increasing the solubility of the soluble organic molecule in water deprived of ionic liquid until reaching a solubility of 1 M by the addition of a stoichiometric amount of ionic liquid relative to the organic molecule.
Beyond a solubility of 0.5 M electroactive organic molecule in a water free of ionic liquid, the electrolyte solutions containing such an organic molecule can be used without adding ionic liquid in a battery.
According to one embodiment, in the method of the invention, said at least one ionic liquid and said at least one organic molecule are each present at a concentration of from 0.1 M to 1 M, preferably 0.1 M at 0.6 M.
Under these concentration conditions, the ionic liquid is an adjuvant within the meaning of the invention and can not be considered as a solvent.
According to one embodiment of the process of the invention, said at least one inorganic salt is an acidic, basic or neutral salt.
According to im embodiment of the process of the invention, said at least one inorganic salt is a strong neutral salt selected from NaCl, KCl, Na2SO4, K2SO4.
According to another embodiment of the process of the invention, said at least one inorganic salt is a strong acid selected from HCl, H 2 SO 4, HClO 4.
The strong acids make it possible to obtain at a high concentration, that is to say at a concentration greater than or equal to 1 M, a conductivity of the high solution, since the charges, anions and protons are completely dissociated. In the sense of the invention, it is possible to define a conductivity as "high" if a current of 1 A flows between two electrodes of 1 cm 2 of surface spaced from each other by 1 cm. This value is obtained when the particle chai'gée in solution is the proton which is the most mobile species of all the ions (then it is OH '). At a pH of less than or equal to I, the pH of the electrolytic solution evolves very little, without the addition of an additive. Under these conditions, only the ions assuage the electrical conductivity of the solution which is then qualified high.
Solutions having a pH greater than 1 and less than or equal to 7 are buffered with an additive comprising a mixture of a weak acid and its conjugate base, i.e. the pH of the solution will evolve very little. The mixtures between a weak acid and its conjugate base and their proportions making it possible to obtain buffer solutions whose pH is of a value greater than 1 at a value of less than or equal to 7 are known to those skilled in the art. . For example, the CH.sub.2 COOH / CH.sub.2 CO.sub.2 O.sub.beta. Mixture makes it possible to obtain buffer solutions whose pH is between 3.8 and 5.8. For solutions having a pH of 1.9 to 3.9, a mixture of ClCH2COOHyClCH2COO ', Na2 may be selected. The buffer solution advantageously comprises a concentration of from 0.1 to 2 M of the mixture between a weak acid and its conjugate base.
In an acidic aqueous solution buffered with the mixture CH 3 COOH / CH 3 COO 3, Na 2, the electrical conductivity is ensured by the mobility of the predominantly present ions, that is to say CH 3 COO 3 and Na 2. Since the CH3COO 'and Na ^ ions are larger than the proton, they move less rapidly in solution and contribute to a decrease in electrical conductivity compared to a non-buffered acidic aqueous solution whose pH is less than or equal to 1. To ensure a good ionic conductivity requires at least a 2M buffer solution which releases 1 M of positive and negative charge in solution.
Finally a conductive buffer solution is highly concentrated in various inorganic and organic ions which is a brake on the solubility of an organic molecule. In this case, the solution can be buffered for example between 0.1 and 0.5 M and the conductivity of the medium is increased by the addition of a neutral inorganic salt.
According to another embodiment of the process of the invention, said at least one inorganic salt comprises two inorganic salts.
According to an advantageous embodiment of the process of the invention, when using at least one ionic liquid, said two inorganic salts are chosen from a neutral inorganic salt and an acidic inorganic salt.
In particular the neutral inorganic salt is selected from NaCl, KCl, Na2SO4, K2SO4 and the acidic inorganic salt is selected from the strong acids HCl, H2SO4, HCIO4.
According to another embodiment of the process of the invention, said at least one inorganic salt is a strong base selected from NaOH, KOH, LiOH. At a pH greater than or equal to 13, the pH of the electrolytic solution evolves very little, without the addition of an additive. Under these conditions, only the ions HO 'ensure the electrical conductivity of the solution.
Solutions with a pH greater than or equal to 7 and less than 13 are buffered using an additive comprising a mixture between a weak base and its conjugated acid, that is to say that the pH of the solution will evolve very little. Mixtures between a weak base and its conjugated acid and their proportions making it possible to obtain buffer solutions whose pH is between a value of greater than or equal to 7 and less than 13 are known to those skilled in the art. The pad also helps to ensure the conductivity of the electrolyte solution. In this case, however, the electrical conductivity remains lower compared to the electrical conductivity of a non-buffered basic solution, but can be increased by the addition of a basic inorganic salt. The use of at least one ionic liquid according to the invention thus involves two inorganic salts.
According to an advantageous embodiment of the process of the invention, said two inorganic salts are chosen from a neutral inorganic salt and a basic inorganic salt.
In particular the neutral inorganic salt is selected from NaCl, KCl, Na 2 SO 4, K 2 SO 4 and the basic inorganic salt is selected from the strong bases NaOH, KOH, LiOH.
In a solution of strong or strong acid, the addition of a strong neutral salt (completely dissociated) can increase the conductivity without increasing the already large quantity (at least 0.5 mol.l -1). in protons or hydroxides.
According to a mode of réahsation of the process of the invention, said inorganic salt is concentration ranging from 0.5 to 3 M, more particularly from 1 M to 2.5 M, preferably 2M.
Below 0.5 M, the amount of ions in the aqueous solution is low enough to reach the conductivity of 40 mS cm -1 of the electrolytic solution of the invention.
Above 3 M inorganic salts, and according to their nature, several phenomena can occur since the electrochemical solutions of the invention are highly charged in molecules and ions (organic molecule + ionic liquid + inorganic salts). Thus, 1) the inorganic salt may be at its solubility limit in the solution under consideration, 2) the inorganic salt may saturate the solution and its excess may cause the insolubility of the organic molecule 3) beyond saturation the inorganic salt can reveal two liquid phases of different density.
According to one embodiment of the process of the invention, said electrolytic solution has an electrical conductivity σ greater than 40 mS-cm -1, in particular greater than 100 mS cm -1, preferably between 100 and 200 mS cm -1. *.
In lowers of 40 mS cm -1 the conductivity becomes low as well as the intensity of the current between two electrodes Thus in an electrolysis process if the current is low the transformation speed of a product will be low and the duration Electrolysis will be very long, and this procedure can not be applicable to an industrial process.
Similarly for a battery or a battery if the conductivity is low the current produced will be low. Conversely, the higher the conductivity, the higher the efficiency of the electrochemical process considered.
According to one embodiment of the process of the invention, said electrolytic solution has a viscosity of 1 to 400 cP measured at 20 ° C with a shear rate of 25 s -1 centipoise is the viscosity of water.
According to an advantageous embodiment of the process of the invention, said electrolytic solution has a viscosity of 1 to 125 cP measured at 20 ° C with a shear rate of 25 s'.
Since the solvent used in the present invention is water, the viscosity of the solution obtained can not be less than 1 cP. The upper limit is set at 125 cP, which corresponds to the viscosity of an electrolyte solution tested in battery mode and showing minimal performance.
According to another advantageous embodiment of the process of the invention, said electrolytic solution has a viscosity of greater than 125 cP at a value of 400 cP, measured at 20 ° C. with a shear rate of 25 seconds. ^
Between a value greater than 125 cP and a value of 400 cP, the electrolytic solution belongs to the invention if the electrical conductivity is greater than 45 mS · cm -1 and the solubility of the organic molecule reaches 0.5 M in aqueous solution. by the addition of an ionic liquid. This electrolytic solution is used in devices other than batteries, such as batteries or electrolysis.
Above 400 cP, the electrical conductivity of the solution can no longer reach 45 mS.cm "Under such conditions, a spontaneous device such as a battery shows minimal performance. Electrolysis is a non-spontaneous process, unlike batteries and batteries, whose energy expenditure will be higher and higher with increasing viscosity. Thus, beyond 400 cP, the energy expenditure related to the implementation of an electrolysis becomes too important for an industrial application.
According to one embodiment of the process of the invention, said electrolytic solution has a half-wave potential of -1.1 V / ECS at -0.7 V / ECS for a basic solution whose hydroxide ion concentration is The invention also relates to an electiOlytic device which comprises at least one ionic liquid, at least one organic molecule, at least one inorganic salt, an aqueous solution and at least one electrode, said at least one at least one ionic liquid and said at least one organic molecule being present in at least substantially stoichiometric amounts.
According to one embodiment of the electrolytic device of the invention, said at least one electrode is selected from porous giaphitic electrodes or metal electrodes preferentially porous nickel.
According to one embodiment, in the device of the invention, said at least one ionic liquid comprises a hydrophilic anion.
According to an advantageous embodiment of the device of the invention, said hydrophilic anion is chosen from methanesulfate anion, ethanesulfate, chloride, iodide, tetrafluoroborate, thiocyanate, dicyanamide, trifluoroacetate, nitrate or hexafluorophosphate.
According to a more advantageous embodiment of the device of the invention, said hydrophilic anion is selected from methanesulfate anion, ethanesulfate, tetrafluoroborate or dicyanamide.
According to one embodiment of the device of the invention, said at least one ionic liquid comprises an aromatic heterocyclic cation,
According to an advantageous embodiment of the device of the invention, said at least one ionic liquid comprises an aromatic heterocyclic cation chosen from an imidazolium, a pyridinium or a quinolinium.
According to an advantageous embodiment of the device of the invention, said at least one ionic liquid comprises a hydrophilic anion and an aromatic heterocyclic cation.
According to a preferred embodiment of the device of the invention, said at least one ionic liquid is chosen from ethanesulfate pyridinium of formula (Ia), ethanesulfate imidazolium of formula (Ib), methanesulfate imidazolium of formula (Ic) , the imidazolium dicyanamide of formula (Id), the imidazolium tetrafluoroborate of formula (Ie) or the quinolinium methanesulfate of formula (If):
According to another embodiment of the device of the invention, said at least one ionic liquid comprises an aliphatic cation.
According to an advantageous embodiment of the device of the invention, said at least one ionic liquid comprises an aliphatic cation chosen from ammonium.
According to an advantageous embodiment of the device of the invention, said at least one ionic liquid comprises a hydrophilic anion and an aliphatic cation.
According to a preferred embodiment of the device of the invention, said at least one ionic liquid is ammonium methanesulfate of formula (I-g):
It is also possible to use several ionic liquids as an adjuvant, in particular according to their properties. Indeed, an ionic liquid may have a high affinity with the organic molecules to be solubilized but its melting point or its viscosity are high to obtain a solution. In this case, a second ionic liquid having more suitable properties may be added to obtain a solution while increasing the solubilizing power of the adjuvant. In this case, the ionic liquid can modulate both the solubility of at least one organic molecule and the viscosity of the electrolytic solution. According to one embodiment of the device of the invention, said electrolytic solution comprises two different ionic liquids.
According to an advantageous embodiment of the device of the invention, said electrolytic solution comprises two different ionic liquids, the two ionic liquids being present in equivalent amount ιηοΐαΐι, and being together in amounts at least substantially stoichiometric with respect to said at least one organic molecule.
According to one embodiment, in the device of the invention, said at least one ionic liquid is present in a volume percentage of from 5 to 20% relative to the total volume of the solution, in particular from 10 to 20%, particularly 10%.
Below 5% by volume, the ionic liquid is not introduced in sufficient quantity relative to the organic molecule to ensure its role of solubilizing adjuvant.
For a value ranging from 5% to less than 10% by volume, the addition of ionic liquid makes it possible to increase the solubility of an organic molecule in the aqueous solution without necessarily reaching the maximum solubility of the organic molecule in the aqueous solution. the water. This maximum is obtained by adding ionic liquid corresponding to 10% by volume relative to the total volume of the solution.
Thus, the solubilization of the organic molecule is obtained in a maximum manner for a stoichiometric ratio equal to 1. On the other hand, when the number of moles of ionic liquid is less than half that of the organic molecule, solubilization is no longer possible. By way of example, alizarin is soluble at a concentration of 0.1 M in an aqueous solution of 2 M KOH. With an addition of 10% of ionic liquid the concentration of alizarin in the aqueous solution of 2 M KOH increases to 0.5 M. However, 5% ionic liquid can solubilize 0.25 M alizarin which coitespond a concentration greater than the concentration of Γalizarin in the aqueous solution of 2 M KOH without addition of ionic liquid but a lower concentration than that obtained by the addition of 10% by volume of ionic liquid.
Above 20% by volume, the ionic liquid is considered a solvent in the sense of the invention. A percentage of ionic liquid greater than 20% by volume relative to the total volume of the solution is therefore not part of the invention.
According to one embodiment of the device of the invention, said at least one organic molecule is polar or apolar.
According to an advantageous embodiment of the device of the invention, said at least one organic molecule is polar.
According to another advantageous embodiment of the device of the invention, said at least one organic molecule is apolar.
According to one embodiment of the device of the invention, said at least one organic molecule is electroactive.
According to one embodiment of the device of the invention, said at least one organic molecule has a molecular weight of from 100 to 600 g.mu.
In this range, organic molecules called "small" and "large" are included. According to one embodiment of the device of the invention, said at least one organic molecule has a molecular weight of from 100 to 200 g.mof
An organic molecule within the meaning of the present invention whose molecular weight is between 100 and 200 g / mol is considered a "small" organic molecule. This class of molecule generally has a solubility in a water free of ionic liquid of 0.2 to 0.5 M.
According to another embodiment of the device of the invention, said at least one organic molecule has a molecular weight of from 200 to 600 g.mof
Organic molecules having a molecular weight of from 200 to 600 g.mu are considered in the meaning of the invention as "large" molecules. Their solubility in water stripped of ionic liquid is generally from 0 M to 0.2 M.
Above 600 g / m 2, the organic molecule induces a too high viscosity of the aqueous solution, decreasing the conductivity of the solution below the threshold of 40 mS cm -1 defining an electrolytic solution within the meaning of the present invention.
According to one embodiment of the device of the invention, said at least one organic molecule has 1 to 4 fused aromatic rings, preferably 1 to 3 fused aromatic rings, more preferably 1 aromatic ring or 3 fused aromatic rings.
Above 4 fused aromatic rings, the intermolecular interactions are too strong to allow an ionic liquid added in at least substantially stoichiometric amount to solubilize the organic molecule in aqueous solution.
According to an advantageous embodiment of the device of the invention, said at least one organic molecule is chosen from the family of quinones, catechols, naphthoquinones, orthonaphthoquinones or anthraquinones.
According to a more advantageous embodiment of the device of the invention, said at least one organic molecule is chosen from the family of quinones, catechols, naphthoquinones or orthonaphthoquinones. The organic molecules of these families belong to the category of "small" molecules within the meaning of the invention.
According to another more advantageous embodiment of the device of the invention, said at least one organic molecule is chosen from the family of anthraquinones.
The molecules of the anthraquinone family belong to the category of "large" molecules.
According to an advantageous embodiment, in the device of the invention, said at least one organic molecule is hydroxylated on at least one position.
The Inventeuia noticed that with the presence of a hydroxyl group close to one of the two carbonyl functions, that is to say in alpha or beta of one of the two carbonyl functions, the electrochemical reversibility of the molecule is assured. In addition, the presence of a hydroxyl function improves the solubility in water and particularly in basic medium.
According to an advantageous embodiment, in the device of the invention, said at least one organic molecule is hydroxylated on at least one position and has a molecular weight of between 100 and 200 g.
According to an advantageous embodiment, in the device of the invention, said at least one organic molecule is hydroxylated at at least one position and has a molecular weight of from 200 to 600 g / mol.
According to a preferred embodiment of the device of the invention, said at least one organic molecule is chosen from the compounds of foimules (II-a) to (II-i):
According to one embodiment of the device of the invention, said at least one organic molecule has a solubility in a water free of ionic liquid ranging from 0 M to a value less than 0.1 M.
The organic molecule thus defined is considered insoluble in a water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase up to 0.1 M of the solubility in a water free of ionic liquid of such an organic molecule when adding equivalent liquid. ionic with respect to the organic molecule.
For the purposes of the present invention, the term "solubility in water without ionic liquid" refers to the solubility of the organic molecule in an aqueous solution, as defined in the present invention, in the absence of ionic liquid.
According to another embodiment of the device of the invention, said at least one organic molecule has a solubility in a water free of ionic liquid ranging from 0.1 M to 0.2 M.
The organic molecule thus defined is considered to be poorly soluble in a water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase of the solubility of the poorly soluble organic molecule in a water without ionic liquid when adding a stoichiometric amount of ionic liquid with respect to the organic molecule. The addition of the ionic liquid increases the solubility of the organic molecule by 3 or 5 in the aqueous solution.
According to another embodiment of the device of the invention, said at least one organic molecule has a solubility in a water free of ionic liquid ranging from 0.2 M to 0.5 M.
The organic molecule thus defined is considered to be soluble in water free of ionic liquid, within the meaning of the present invention. The invention is based in particular on the unexpected observation of the inventors of the increase of the solubility of the soluble organic molecule in a water free of ionic liquid until reaching a solubility of 1 M by the addition of a stoichiometric amount of ionic liquid with respect to the organic molecule.
Beyond a solubility of 0.5 M electroactive organic molecule in a water free of ionic liquid, the electrolyte solutions containing such an organic molecule can be used without adding ionic liquid in xme battery.
According to one embodiment, in the device of the invention, said at least one ionic liquid and said at least one organic molecule are each present at a concentration of from 0.1 M to 1 M, preferably from 0, 1 M to 0.6 M.
Under these concentration conditions, the ionic liquid is an adjuvant within the meaning of the invention and can not be considered as a solvent.
According to one embodiment of the device of the invention, said at least one inorganic salt is an acidic, basic or neutral salt.
According to one embodiment of the device of the invention, said at least one inorganic salt is a strong neutral salt selected from NaCl, KCl, Na 2 SO 4, K 2 SO 4.
According to another embodiment of the device of the invention, said at least one inorganic salt is a strong acid selected from HCl, H 2 SO 4, HClO 4,
The strong acids make it possible to obtain at a high concentration, that is to say at a concentration greater than or equal to 1 M, a conductivity of the high solution, since the charges, anions and protons are completely dissociated. In the sense of the invention, it is possible to define a conductivity as "high" if a current of 1 A flows between two electrodes of 1 cm 2 of surface distant from each other by 1 cm. This value is obtained when the particle charged in solution is the pruton which is the most mobile species of all the ions (then it is OH '). At a pH of less than or equal to 1, the pH of the electrolytic solution evolves very little, without the addition of an additive. Under these conditions, only the ET ions ensure the electrical conductivity of the solution which is then qualified to be high.
Solutions having a pH greater than 1 and less than or equal to 7 are buffered with an additive comprising a mixture of a weak acid and its conjugate base, i.e. the pH of the solution will evolve very little. Mixtures between a weak acid and its conjugate base and their proportions making it possible to obtain buffer solutions whose pH is from a value greater than 1 to a value of less than or equal to 7 are known to those skilled in the art. . For example, the mixture CH 3 COOH / CH 3 COO 3, Na 2 makes it possible to obtain buffer solutions whose pH is between 3.8 and 5.8 For solutions with a pH ranging from 1.9 to 3.9, a ClCH 2 COOH / CICH 2 COO 3, Na 2 mixture may be chosen, the buffer solution advantageously comprising a concentration of from 0.1 to 2 M of the mixture between a weak acid and its conjugated base.
In an acidic aqueous solution buffered with the mixture CH 3 COOH / CH 3 COO 3, Na 2, the electrical conductivity is ensured by the mobility of the predominantly present ions, that is to say CH 3 COO 3 and Na 2. The CH 3 COO 3 and Na 2+ ions being larger than the HL piuton, they move less rapidly in solution and contribute to a decrease in electrical conductivity compared to a non-buffered acidic aqueous solution whose pH is less than or equal to 1. To ensure good ionic conductivity, at least a 2M buffer solution is required, which releases 1M of positive and negative charge in solution.
Finally, a conductive buffer solution is highly concentrated in various inorganic and organic ions which is a good for the solubility of an organic molecule. In this case, the solution can be buffered for example between 0.1 and 0.5 M and the conductivity of the medium is increased by the addition of a neutral inorganic salt.
According to another embodiment of the device of the invention, said at least one inorganic salt comprises two inorganic salts.
According to an advantageous embodiment of the device of the invention, when using at least one ionic liquid, said two inorganic salts are chosen from a neutral inorganic salt and an acidic inorganic salt.
In particular the neutral inorganic salt is selected from NaCl, KCl, Na2SO4, K2SO4 and the acidic inorganic salt is selected from the strong acids HCl, H2SO4, HCIO4.
According to another embodiment of the device of the invention, said at least one inorganic salt is a strong base selected from NaOH, KOH, LiOH. At a pH greater than or equal to 13, the pH of the electrolytic solution evolves very little, without the addition of an additive. Under these conditions, only the ions HO 'ensure the electrical conductivity of the solution.
Solutions with a pH greater than or equal to 7 and less than 13 are buffered using an additive comprising a mixture between a weak base and its conjugated acid, that is to say that the pH of the solution will evolve very little. Mixtures between a weak base and its conjugated acid and their proportions making it possible to obtain buffer solutions whose pH is between a value of greater than or equal to 7 and less than 13 are known to those skilled in the art. The pad also helps to ensure the conductivity of the electrolyte solution. In this case, however, the electrical conductivity remains lower compared to the electrical conductivity of a non-buffered basic solution but can be increased by the addition of a basic inorganic salt. The use of at least one ionic liquid according to the invention thus involves two inorganic salts.
According to an advantageous embodiment of the device of the invention, said two inorganic salts are chosen from a neutral inorganic salt and a basic inorganic salt.
In particular the neutral inorganic salt is selected from NaCl, KCl, Na 2 SO 4, K 2 SO 4 and the basic inorganic salt is selected from the strong bases NaOH, KOH, LiOH.
In a solution of strong acid or strong base the addition of a strong neutral salt (completely dissociated) makes it possible to increase the conductivity without increasing the already important quantity (at least 0,5 rnoLL '*) in protons or hydroxides .
According to one embodiment of the device of the invention, said inorganic salt is of concentration ranging from 0.5 to 3 M, more particularly from 1 M to 2.5 M, preferably 2M.
Below 0.5 M, the amount of ions in the aqueous solution is too small to reach the conductivity of 40 mS cm -1 of the electrolytic solution of the invention.
Above 3 M inorganic salts, and according to their nature, several phenomena can occur since the electrolytic solutions of the invention are highly charged in molecules and ions (organic molecule + ionic liquid + inorganic salts). Thus, 1) the inorganic salt can be at its solubility limit in the solution under consideration, 2) the inorganic salt can saturate the solution and its excess can cause the insolubility of the organic molecule 3) beyond saturation the inorganic salt can reveal two liquid phases of different density.
According to one embodiment of the device of the invention, said electrolytic solution has an electrical conductivity σ greater than 40 mS.cm '*, especially greater than 100 mS.cm' ', preferably between 100 and 200 mS. cm'V
Below 40 mS cm -1, the conductivity becomes low as well as the intensity of the current between two electrodes, so in an electrolysis process if the coupling is weak the rate of transformation of a product will be low and the duration Electrolysis will take a very long time and this procedure can not be applied to an industrial process.
Similarly for a battery or a battery if the conductivity is low the current produced will be low. On the other hand, the higher the conductivity, the higher the efficiency of the electrochemical process considered sem high.
According to one embodiment of the device of the invention, said electrolytic solution has a viscosity of from 1 to 400 cP measured at 20 ° C with a shear rate of 25 s ''. 1 centipoise is the viscosity of water.
According to an advantageous embodiment of the device of the invention, said electrolytic solution has a viscosity of 1 to 125 cP measured at 20 ° C with a shear rate of 25 s'.
Since the solvent used in the present invention is water, the viscosity of the solution obtained can not be less than 1 cP. The upper limit is set at 125 cP, which corresponds to the viscosity of an electrolyte solution tested in battery mode and showing minimal performance.
According to another advantageous embodiment of the device of the invention, said electrolytic solution has a viscosity of greater than 125 cP at a value of 400 cP, measured at 20 ° C. with a shear rate of 25 seconds. ^
Between a value greater than 125 cP and a value of 400 cP, the electrolytic solution belongs to the invention if the electrical conductivity is greater than 45 mS · cm -1 and the solubility of the organic molecule reaches 0.5 M in aqueous solution. by the addition of an ionic liquid. This electrolytic solution is used in devices other than batteries, such as batteries or electrolysis.
Above 400 cP, the electrical conductivity of the solution can no longer reach 45 mS.cm.sup.2. Under such conditions, a spontaneous device such as a battery shows minimal performance. Electrolysis is a non-spontaneous process, unlike batteries and batteries, whose energy expenditure will be higher and higher with increasing viscosity. Thus, beyond 400 cP, the energy expenditure related to the implementation of an electrolysis becomes too important for an industrial application.
According to one embodiment of the device of the invention, said electrolytic solution has a half-wave potential of -1.1 V / ECS at -0.7 V / ECS for a basic solution whose hydroxide ion concentration is The invention also relates to the use of the electrolytic device of the invention for the implementation of an electrochemical storage method.
According to one embodiment, the use of the electrolytic device of the invention is an electrolysis. "Electrolysis" is a non-spontaneous electrochemical process that induces a chemical transformation by the passage of electric current through a substance.
According to one embodiment, the use of the electrolytic device of the invention is for the preparation of a battery or a battery.
For the purposes of the present invention, the term "battery" means that two electroactive substances, each soluble in an electrolysis solution, react chemically in contact with the electrodes to provide electrical energy. The two electroactive substances transfoimées can be regenerated by electrolysis by reversing the flow direction of the solutions.
A "battery" refers to a device in which two electroactive substances, each soluble in an electrolytic solution, react chemically with the electrodes to provide electrical energy. At least one of the two transformed electroactive substances can not be regenerated by electrolysis by reversing the flow direction of the solutions. The device is irreversible unlike a battery which is a reversible device.
Batteries and batteries are devices whose operation is spontaneous, unlike electrolysis devices.
According to one embodiment, the use of the electrolytic device of the invention is for the implementation of an electrochemical storage method; in particular said electrochemical storage taking place in a battery or a battery, in particular a circulating electrolyte molecular battery or a circulating electrolyte molecular battery.
According to one embodiment, in the use of the electrolytic device of the invention, said battery is a circulating electrolyte molecular battery. The term "molecular battery" means that the chemical reactions are catalyzed by organometallic catalysts blocked on at least one electrode. This expression also means that electroactive substances are organic molecular compounds.
The term "circulating electrolyte" means that the electrolytic solutions percolate through two porous electrodes. Both solutions are stored in a tank.
The purpose of using the electrolytic device of the invention in a circulating electrolyte battery is to increase the energy storage through a better solubilization of the active species.
Indeed, an important role attributable to batteries with circulating electrolyte is support for renewable energies (wind and photovoltaic) to regulate the consumption of electrical energy. In the presence of wind or sun, the energy released is directly used and the surplus stored by a circulating electrolyte battery. When the wind or the brightness is not enough, it is the battery which ensures the production in energy. For example, depending on the volume of the tanks this system of exchange and regulation is conceivable to ensure the energy independence of a house, an eco-district, a farm, a factory.
The principle of a circulating electrolyte molecular battery, FIG. 5, is based on the circulation of an aqueous solution through a porous electrode. The oxidant (0x1) and the reductant (Red2) in contact with a catalyst immobilized on the electrode generate the electronic transfers leading to the appearance of an electric current. The advantages of this battery are multiple and reside mainly by the fact of using an aqueous solution, to work instantly as soon as the fluid flows, to have an electrical capacity directly connected to the volumes of the storage tanks and to work with regenerable solutions .
The important point from this conception is that the amount of available energy (Joule or Watt.hour) and the developed power (watt) is optimized independently. Indeed: - The power of the battery is connected to the potential difference between the two redox couples and the surface of the electrodes. The power of the battery depends on the size and nature of the electrodes. - The amount of energy is related to the volumes of the reservoirs and the concenü'ation of redox couples.
The amount of stored electricity is therefore related to the amount of electroactive organic molecule (example: quinone, anthraquinone, etc.) dissolved in the electrolytic solution. As a result, the amount of electricity is proportional to the solubility of the electroactive organic molecule and the volume of the reservoir in which the molecule is solubilized. The invention, as well as the various advantages that it presents, will be more easily understood thanks to the following description of nonlimiting embodiments thereof given with reference to the figures, in which: FIG. cyclic voltammogram Alizarin RedS A) without addition of ionic liquid and B) with 0.6 M ionic liquid, obtained with a scanning speed of 100 mVs' ^ the working electrode being a vitreous carbon electrode ; FIG. 2 represents the evolution of the cyclic voltammogram of 0.6M alizarin RedS in a 0.2 M aqueous solution of KOH as a function of the volume of ionic liquid added (Electrode = glassy carbon, scanning speed = 100mV.s · '); FIG. 3 shows the evolution of the cyclic voltammogram of 0.6M alizarin RedS in the presence of 0.6 M of ionic liquid, as a function of the number of equivalents of added KOH. 1 equivalent corresponds to 0.6 M KOH (Electrode = glassy carbon, scanning speed = 100 mV.sup.-1); FIG. 4 represents the evolution of the cyclic voltammogram of the 0.6 M alizain RedS in a 0.6 M aqueous solution of KOH as a function of the KCl concentration (Electrode = glassy carbon, scanning speed = 100 mV-s'); FIG. 5 represents the operating principle of a circulating electrolyte molecular battery.
EXAMPLES
Synthesis of ionic liquids
Ionic liquids are obtained by following the conventional synthesis scheme described many times in the literature. In the case of ionic liquids with sulfate anion, the compound serving as a base for the cation (e.g. imidazole, amine, etc.) and directly reacted with a dialkyl sulphate (Green Chem 2012, 14, 725). In the case of other anions (eg dicyanamide, tetrafluoroborate), the compound serving as base for the cation is reacted with an alkyl halide (eg bromobutane) during a so-called quaternization phase, and then the salt obtained is engaged. in anionic metathesis with the salt corresponding to the targeted anion (eg sodium tetrafluoroborate) (Gi'een Chem 2005, 7, 39).
Table 1 groups together three ionic liquids used in the present invention.
Table 1: Ionic Liquids Used in the Invention Method of Cyclic Voltammetry The action of ionic liquids on the solubility of organic molecules can be observed by simple electrochemical analysis. The method used is voltammetry with linear variation of the potential. The result is the plot of a curve i = f (E) whose value of the oxidation or reduction current of the electroactive molecule is proportional with its concentration in solution.
The electrochemical analyzes are carried out in an electrochemical cell whose volume is 40 ml. The volume of the solutions introduced into the electrochemical cell is 10 ml. To perform the analyzes, three electrodes immersed in the solution are used: - Working electrode. The working electrode is the seat of the electrochemical reaction studied. In this work a glassy carbon electrode with a surface area of 3 mm diameter or a nickel electrode of 5 mm diameter was used. Electrochemical reactions are often sensitive to the nature of the electrodes. For example, depending on their nature, some electrodes may passivate and others not, vis-à-vis the same electrochemical system in solution.
Counter electrode; the counter electrode allows the flow of the current in the solution between itself and the working electrode. This electrode must be very stable (for example, do not dissolve in oxidation). To maintain stability the counter electrode is platinum (it is a platinum film 1 mm in diameter). - Reference electrode. This electrode allows the potential applied to the working electrode to be monitored by measuring the potential difference between itself and the working electrode. The particularity of a reference electrode is to have a potential that is fixed. Thus the potential of the working electrode is referenced with respect to the reference electrode used. The reference electrode used in this work is a saturated calomel electrode whose potential; E = 0.248 V / ESH.
These three electrodes are connected to an "SP50" potentiostat from Biologie. The potentiostat is controlled by a computer via the EClab software of Biology.
The electrochemical responses obtained are very similar regardless of the ionic liquid used (1-a), (I-b) or (I-c) to dissolve an organic molecule. The following examples are applicable to each ionic liquid (I-a), (I-b) and (I-c).
Protocol for Maximum Solubility Testing of Organic Compounds of Interest in Ionic Liquid Mixtures / Basic Water Solution (Vial Method) 1Omg of the targeted organic compound is introduced into a vial along with the desired amount of ionic liquid to be tested. A basic aqueous solution is added in portions of 0.1 ml until a solution is obtained. The maximum concentration is then determined according to the following formula;
Cmax [nicomposed J ^ hicomposedJfV
Cmax is the maximum concentration of organic molecule given in mol. The decomposition is the mass of the organic molecule introduced (in g), the compound is the molar mass of this organic molecule (in g.mor ^) and V is the volume of aqueous solution added (in L).
Protocol for the solubilization of quinone derivatives in an ionic liquid mixture / basic aqueous solution in the presence of hydroxide ions
The quinone is introduced into a volumetric flask (the quantity depends on the concentration in question, generally between 0.1 and 0.5 M). The liquid is added (the amount depends on the solubilizing power of the ionic liquid, in stoichiometric amount relative to the quinone). An aqueous solution containing hydroxide ions at a concentration of 0.1 and 5 M is added until completion to the gauge. The mixture is then placed for 5 minutes in an ultrasonic bath to ensure good dispersion of the compounds. This mixture is then observed under a binocular microscope and if a doubt about the solubility remains (eg in the case of a too colored solution), a filtration under reduced pressure on membrane PES (polyethersulfone) is carried out to ensure that no particle is in suspension.
Measurement of the viscosity of the solutions
The viscosities of the solutions are measured using an Anton Paar MCR301 rheometer at a temperature of 20 ° C. and a shear rate of 25%.
Conductivity measurements of solutions
The conductivities of the solutions are measured using a Tucassel CDRV 62 conductivity meter at a temperature of 20 ° C.
EXAMPLE 1 alizarin redS is an anthraquinone whose solubility is of the order of 0.2 mol.L "* in a solution of potassium hydroxide (KOH) at a concentration of 2 mol.l '* in the presence of 0.6 M of liquid ionic the solubility of alizarin is increased to 0.6 mol.L' ^
The concentration of the ionic liquid is 0.6 me.l *, identical to that of alizarin redS. The increase in solubility results in a significant increase in peak oxidation intensity and peak reduction by a factor of 15 (Figure 1). The intensity obtained is slightly greater than 60 mA.cm "^ which is very high and is a reflection of a very large amount of dissolved material in the vicinity of the electrode.
Example 2
FIG. 2 represents the evolution of the electrochemical response of alizarin redS as a function of the volume of ionic liquid added. The percentage by volume is calculated with respect to the total volume of the solution. Under these conditions, 10% by volume represents an addition in stoichiometric amounts with alizarin redS. In the meaning of the invention, alizarin redS is a "large" molecule of low solubility in water free of ionic liquid.
For volume additions greater than 10% the electrochemical response weakens strongly. This phenomenon is related to an excess of ionic liquid whose consequence is to cause a decrease in the electrical conductivity of the solution. Beyond the stoichiometric ratio (10% by volume) the electrical resistance of the solution (ohmic drop) increases very rapidly. Under these conditions these mixtures become unsuitable for use in an electrochemical process developing strong currents. Conversely for a percentage less than 10% the electro-chemical response is improved. But, quickly the solution becomes more and more "pasty" to finish after a few minutes to freeze. The ionic liquid added in an amount of less than 0.8 equivalent of organic molecule is no longer capable of fulfilling its role as a solubilizer.
Example 3
Table 2 summarizes the results of a series of solubilization molecules belonging to the family of anthraquinones.
Table 2: Influence of solubility of anthraquinones as a function of ionic liquid concentration
In all these examples, the addition of an ionic liquid of formula (I-a), (I-b) or (I-c) increases the solubility of the anthraquinones. The concentration of ionic liquid at least is equal to the concentration of anthinquinone (case of anthraquinones # 2, 3, 4 and 5). An excess of ionic liquid is necessary for anthraquinones whose natural solubility in a solution at pH = 14 is very low (case of anthraquinones # 1, 6,7 and 8).
Example 4
In 2M KOH, in a 1: 1 ratio with azarine, 1,3-dimethylimidazolium methylsulfate gives a solution with a concentration greater than 0.5M whereas N-methylisoquinolinium methylsulfate does not allow it (a precipitate is always visible at 0.5M). Similarly, when the proportion of 1,3-dimethylimidazolium methylsulfate relative to alizarin is less than 1: 1, a precipitate is always visible at 0.5M. When a mixture of these two ionic liquids is used in the following proportions: A zarine / 1,3-dimethylimidazolium methylsulfate / N-methylisoquinolinium methylsulfate 1: 0.5: 0.5, a 0.8M concentration solution is obtained while the two isolated ionic liquids used in the same proportions (Alizarin / ionic liquid 1: 0.5) do not make it possible to obtain a solution at 0.5M. This observation is repeated with an Alizaiine / methylsulfate mixture of N, N-diisopropylethylmethylammonium / N-methylisoquinoline 1: 0.5: 0.5 methylsulphate.
Example 5
Figure 3 is a study of the electrochemical response of alizarin red S (anthraquinone No. 5) as a function of the concentration of KOH. The hydroxide ions (OB ') intervene in the equilibrium of autoprotonation of the water which is the main solvent of the electrolytic solution. Given the concentrations of hydroxides (OH ') put stake at stake the pH of the solution which is of the order of 14 is difficult to calculate and difficult to measure,
The concentration of ionic liquid of formula (Ia) is 0.6 mol.L' * for a concentration of alizarin red S of 0.6 me.L 'A strong addition of KOH does not interfere with the principle of solubilization at ionic liquids and significantly enhances the electrochemical response.
This result is important because the solubilization technique by ionic liquids can be done in solutions whose ionic strength reaches non-standard values, which is quite favorable for using them as electrolytic solution.
Assuming free ions between them Table 3 collects the values of the ionic strength (I) as a function of the concentration of KOH.
Table 3: Evolution of the ionic strength as a function of the concentration of KOH.
With Ci = concentration of the ion i Zj = valence of the ion i
And: [L.L] = 0.6 mol.L "^; [A redS ', Na ^] = 0.6 molL *
The ions present in the solution are monovalent therefore the ionic strength also reflects the molar concentration in positive and negative charges. For such concentrations, the ionic conductivity of each solution largely supports 1A currents applied between two electrodes 1 cm apart.
Finally, an increase in the electrical activity of the solution related to the increase in the concentration of ions (OH ') resulting from the equilibrium of autoprotolysis of water (solvent) exacerbates the electrochemical response of alizarin red S, (Figure 3). It is important to note also that even in the presence of an excess of KOH (quantity greater than 2 equivalents), the solubility provided by the ionic liquid / organic molecule interaction is not influenced,
Example 6
In this example, the electiochemical response of alizarin redS is studied as a function of the concentration of KCl. The concentrations of alizarin redS, KOH and ionic liquid are identical is set at 0.6 mol.L 'Table 4 presents the value of the ionic strength for different concentrations in KCl.
Table 4: Evolution of the ionic strength as a function of the KCl concentration.
A strong addition of KCl does not interfere with the principle of solubilization using ionic liquids. The electrochemical response, Figure 4 is significantly increased to an ionic strength of about 1 to stabilize beyond this value.
This example shows that for a fixed pH, a solution comprising a solubilized solubilized by the technique of ionic liquids may exhibit a variable electrochemical response depending on the addition of a neutral salt. This phenomenon confirms that the interactions between ionic liquid and anthraquinone are effective.
This solubilization technique makes it possible to work with solutions concentrated in ions, which makes it possible while keeping the solubility constant to increase the electrical conductivity of the solution by adding a neutral conducting salt such as KCl, NaCl, NaBp4, Na2SO4 , K2SO4 .....
Example 7
Table 5: Measurements of the half-wave potential, the conductivity and the viscosity of different electrolytic solutions.
Composition of the solutions:
Solution 1: 2,5-Dihydroxy-1,4-benzoquinone (II-i) 0.83M; 1,3-dimethylimidazolium methylsulfate (1-c) 0.83M; KOH 2M
Solution 2: Alizarin (II-d) 0.5M; 1,3-dimethylimidazolium methylsulfate (I-c)
0.5M; KOH2M
Solution 3: Alizarin Red S (II-e) 0.6M; 1,3-dimethylimidazolium methylsulfate (I-c) 0.6M; KOH 2M
Solution 4: Alizarin (Π-d) 0.5M; 1,3-dimethylimidazolium methylsulfate (I-c) 0.25M; N-methylisoquinolinium methylsulfate (I-Q 0.25M, 2M KOH
Solution 5: Alizarin (H-d) 0.5M; N, N-methylsulfate
diisopropylethylimethylammonium (I-g) 0.5M; KOH 2M
Solution 6: Alizarin (II-d) 0.5M; 1,3-dimethylimidazolium methylsulfate (I-c) 0.5M; 3M KOH
Solution 7: Alizarin (II-d) 0.5M; 1-methyl-3-butylimidazolium dicyanamide (I-d) 0.5M; KOH 2M
Solution 8: Alizarin (Π-d) 0.5M; 1-methyl-3-butylimidazoline (1-e) teti'afluoroborate 0.5M; KOH 2M
Solution 4 is an example of a mixture of ionic liquid illustrating the modulation of the properties of the electrolyte solution as a function of the ionic liquids. In comparison with solution 2 (same organic molecule, ionic liquid in common), the aqueous solubility of the organic molecule is identical however the conductivity of solution 4 is reduced and its viscosity is greatly increased. This example shows that the nature of the ionic liquid (besides the effect of solubilization) significantly influences the viscosity of the medium. Solution 5 is an example of the use of an ionic liquid comprising an aliphatic cation.
With regard to solution 2, solution 6 comprises the same constituents but has an increase in the inorganic salt, KOH. This solution has an increase in conductivity but decreases the viscosity. Depending on the use of the intended solution, therefore, a compromise is usually required between high conductivity (greater than 50 mScm -1) and low viscosity (less than 125cP).
With regard to solution 2, solution 7 corresponds to a flag modification of the ionic liquid qm makes it possible to reduce by a factor of 10 the viscosity of the solution. Thus, the conductivity can be increased with an increase in the OH ion concentration without any effect on the viscosity. Solution 8 illustrates the same phenomenon.

权利要求:
Claims (10)
[1" id="c-fr-0001]
CLAIMS L Use of at least one ionic liquid to increase the solubility of at least one organic molecule in aqueous solution containing at least one inorganic salt and obtain an electrolytic solution, wherein said at least one ionic liquid and said at least one molecule organic compounds are present in said aqueous solution in at least substantially stoichiometric amounts.
[2" id="c-fr-0002]
2. Use of at least one ionic liquid according to claim 1, said at least one ionic liquid comprising a hydrophilic anion and an aromatic heterocyclic cation or an aliphatic cation; said hydrophilic anion being in particular chosen from the anion méianesulfate, ethanesulfate, chloride, iodide, tetrafluoroborate, thiocyanate, dicyanamide, trifluoroacetate, nitrate or hexafluorophosphate, preferably selected from ranion methanesulfate, ethanesulfate, tetrafluoroborate or dicyanamide; said aromatic heterocyclic cation being in particular chosen from an imidazolium, a pyridinium or a quinolinium; or said aliphatic cation being in particular chosen from an ammonium; said at least one ionic liquid being more preferably selected from pyridinium ethanesulfate of formula (Ia), imidazolium ethanesulfate of formula (Ib), imidazolium methanesulfate of formula (Ic), dicyanamide imidazolium of formula (1-d), tetrafluoroborate imidazolium of formula (Ie) j, quinolinium methanesulfate of formula (If), or ammonium methanesulfate of formula (Ig):




[3" id="c-fr-0003]
3. Use of at least one ionic liquid according to one of claims 1 or 2, said at least one ionic liquid being present in a volume percentage of between 5 and 20% relative to the total volume of the solution, in particular of 10 to 20%, especially 10%.
[4" id="c-fr-0004]
4. Use of at least one ionic liquid according to one of claims 1 to 3, said at least one organic molecule being polar or apolar; and / or said at least one organic molecule being electroactive; and / or said at least one organic molecule having a molecular weight of from 100 to 600 gmol in particular of from 100 to 200 g-mol * or from 200 to 600 g-mol "'and / or said at least one an organic molecule having in particular 1 to 4 fused aromatic rings, preferably 1 to 3 fused aromatic rings, more preferably 1 aromatic ring or 3 fused aromatic rings, and / or said at least one organic molecule being hydroxylated on at least one position; in particular, said at least one organic molecule being chosen from the family of quinones, catechols, n-α-htoquinones, orthonaphthoquinones or anthraquinones, preferably chosen from compounds of formulas (Π-a) to (Ui):




[5" id="c-fr-0005]
5. Use of at least one ionic liquid according to one of claims 1 to 4, said at least one organic molecule having a solubility in water with ionic liquid of 0 M to less than 0.1 M; or said at least one organic molecule having solubility in water with no ionic liquid of 0.1 M to 0.2 M; or said at least one organic molecule having a solubility in a water free of ionic liquid of 0.2 M to 0.5 M.
[6" id="c-fr-0006]
6. Use of at least one ionic liquid according to one of claims 1 to 5, said at least one inorganic salt being an acidic salt, basic or neutral; in particular, said at least one inorganic salt being a strong neutral salt selected from NaCl, KCl.Na 2 SO 4 K 2 SO 4, or said at least one inorganic salt being a strong acid selected from HCl, H 2 SO 4, HClO 4, especially said at least one inorganic salt. comprising two inorganic salts, in particular chosen from a neutral inorganic salt and an acidic inorganic salt, preferably the neutral inorganic salt being selected from NaCl, KCl, Na2SO4, K2SO4 and the acidic inorganic salt being selected from the strong acids HCl, H2SO4, HCIO4 ; or said at least one inorganic salt being a strong base selected from NaOH, KOH, LiOH, especially said at least one inorganic salt comprising two inorganic salts, in particular selected from a neutral inorganic salt and a basic inorganic salt, preferably the neutral inorganic salt being selected from NaCl, KCl, Na2SO4, K2SO4 and the basic inorganic salt being selected from strong bases NaOH, KOH, LiOH; in particular said inorganic salt being of concentration ranging from 0.5 to 3M, more particularly from 1M to 2.5M, preferably 2M.
[7" id="c-fr-0007]
7. Use of at least one ionic liquid according to one of claims 1 to 6, said electrolytic solution having an electrical conductivity σ greater than 40 mS.cm '', especially greater than 100 mS.cm "S preferably comprised of 100 to 200 mS.om · ^ and / or said electrolytic solution having a viscosity of 1 to 400 cP measured at 20 with a shear rate of 25 s' including 1 to 125 cP measured at 20 ° C with a shear rate of 25 seconds, or of greater than 125 cP at 400 cP, measured at 20 ° C with a shear rate of 25 seconds; and / or said electrolytic solution having a half wave potential of -1.1 V / ECS at "0.7 V / ECS for a basic solution whose hydroxide ion concentration is greater than 0.5 mol.L ' *.
[8" id="c-fr-0008]
8. A process for aqueous solubilization of at least one organic molecule by the use of at least one ionic liquid in one of the revoadications 1 to 7, comprising a step of adding said at least one organic molecule and said at least one ionic liquid in at least substantially stoichiometric amounts in an aqueous solution that may contain an inorganic salt, said addition step being followed or preceded by a step of solubilizing at least one inorganic salt in said aqueous solution.
[9" id="c-fr-0009]
9. Di ^) electrolytic support which comprises the electrolytic solution according to one of claims 1 to 7 comprising at least one ionic liquid, at least one organic molecule, at least one inorganic salt, an aqueous solution and at least one electrode, said at least one ionic liquid and said at least one organic molecule being present in at least substantially stoichiometric amounts.
[10" id="c-fr-0010]
10. Use of the electrolytic device according to claim 9 for the implementation of an electrochemical storage method; in particular said electrochemical storage taking place in a battery or a battery, in particular a circulating electrolyte molecular battery or a circulating electrolyte molecular battery

类似技术:

---

公开号 | 公开日 | 专利标题

---

FR3052598A1|2017-12-15|USE OF IONIC LIQUIDS AS ADJUVANT IN ELECTROCHEMISTRY

---

Zhuo et al.2013|Salts of C60 | 8 electrodeposited onto a glassy carbon electrode: surprising catalytic performance in the hydrogen evolution reaction

---

Baghayeri et al.2013|Determination of nifedipine using nanostructured electrochemical sensor based on simple synthesis of Ag nanoparticles at the surface of glassy carbon electrode: application to the analysis of some real samples

---

AU2011276362B2|2016-03-17|Novel catalyst mixtures

---

Taleat et al.2008|Electrochemical behavior of ascorbic acid at a 2, 2′-[3, 6-dioxa-1, 8-octanediylbis |]-bis-hydroquinone carbon paste electrode

---

Lehr et al.2011|Spontaneous grafting of nitrophenyl groups to planar glassy carbon substrates: evidence for two mechanisms

---

Bahadori et al.2016|Investigation of ammonium-and phosphonium-based deep eutectic solvents as electrolytes for a non-aqueous all-vanadium redox cell

---

Martinez-Perinan et al.2016|Insulin sensor based on nanoparticle-decorated multiwalled carbon nanotubes modified electrodes

---

Manjuntha et al.2019|Electrooxidation and determination of estriol using a surfactant modified nanotube paste electrode

---

Teixeira et al.2009|An electrochemical sensor for dipyrone determination based on nickel-salen film modified electrode

---

Jiang et al.2009|Probing anodic reaction kinetics and interfacial mass transport of a direct formic acid fuel cell using a nanostructured palladium–gold alloy microelectrode

---

Gorostiza et al.2003|Electrochemical characterization of the open-circuit deposition of platinum on silicon from fluoride solutions

---

Yi et al.2010|Novel nanoporous binary Ag-Ni electrocatalysts for hydrazine oxidation

---

EP2922987B1|2016-09-21|Method for coating the surface of an organic or metal material with particular organic compounds by means of a pulsed-current electrochemical reduction of the diazonium ions of said organic compounds

---

Tahmasebi et al.2018|Highly efficient electrochemical determination of propylthiouracil in urine samples after selective electromembrane extraction by copper nanoparticles-decorated hollow fibers

---

Alabdullah et al.2020|Evidence supporting an emulsion polymerisation mechanism for the formation of polyaniline

---

Sanborn et al.2019|Interfacial and nanoconfinement effects decrease the excited-state acidity of polymer-bound photoacids

---

FR2992235A1|2013-12-27|HOLLOW PLATINUM NANOPARTICLES FOR FUEL CELLS

---

Mohadesi et al.2011|A new negative charged self-assembled monolayer for selective electroanalytical determination of dopamine in the presence of ascorbic acid

---

Elliott et al.2001|Electrochemical characterization of a templated insulating polymer-modified electrode

---

Giao et al.2019|Au nanodendrite incorporated graphite pencil lead as a sensitive and simple electrochemical sensor for simultaneous detection of Pb |, Cu | and Hg |

---

Kalaivani et al.2018|Fabrication of CdSe quantum dots@ nickel hexacyanoferrate core–shell nanoparticles modified electrode for the electrocatalytic oxidation of hydrazine

---

Tsai et al.2011|Electrodeposited indigotetrasulfonate film onto glutaraldehyde-cross-linked poly-l-lysine modified glassy carbon electrode for detection of dissolved oxygen

---

González-Fuentes et al.2012|Radical grafting of carbon surfaces by oxidation of 5-nitroindole derived anions

---

Choi et al.2021|Temporally Resolved Electrochemical Interrogation for Stochastic Collision Dynamics of Electrogenerated Single Polybromide Droplets

同族专利:

---

公开号 | 公开日

---

CA3025139A1|2017-12-14|

---

US20190148754A1|2019-05-16|

---

EP3469647A1|2019-04-17|

---

CN109643817A|2019-04-16|

---

WO2017212179A1|2017-12-14|

---

JP2019520677A|2019-07-18|

---

FR3052598B1|2018-06-01|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

JP2010086935A|2008-09-03|2010-04-15|Sharp Corp|Redox flow battery|

---

WO2010094657A1|2009-02-18|2010-08-26|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Method for storing electrical energy in ionic liquids|

---

JP2014127358A|2012-12-26|2014-07-07|Nihon Univ|Redox flow battery|

---

WO2015053588A1|2013-10-11|2015-04-16|서울대학교산학협력단|Electrolyte solution for redox flow battery and redox flow battery comprising same|

---

US20160233536A1|2013-10-11|2016-08-11|Seoul National University R&Db Foundation|Electrolyte Solution for Redox Flow Battery and Redox Flow Battery Comprising Same|

---

FR2935547B1|2008-08-29|2011-03-25|Commissariat Energie Atomique|IONIC LIQUID ELECTROLYTES AND ELECTROCHEMICAL DEVICES SUCH AS ACCUMULATORS COMPRISING SAME.|

---

JP2011236161A|2010-05-11|2011-11-24|Mazda Motor Corp|Ionic liquid, method for producing the same, power storage device using the same|

---

CN103904362A|2012-12-24|2014-07-02|北京有色金属研究总院|Preparation method and application of ionic liquid electrolyte of safety-type lithium ion battery|

---

CN104781977B|2013-07-05|2019-07-16|松下电器产业株式会社|Electrochemical energy storage device|

---

US9941559B2|2014-11-11|2018-04-10|Toyota Motor Engineering & Manufacturing North America, Inc.|Water enhanced ionic liquid electrolytes for metal-air batteries|US11133523B2|2017-07-28|2021-09-28|Toyota Motor Engineering & Manufacturing North America, Inc.|Aqueous electrolytes with protonic ionic liquid and batteries using the electrolyte|

---

EP3766118A1|2018-03-12|2021-01-20|KIST-Europe Forschungsgesellschaft mbH|Aqueous composition as electrolyte comprising ionic liquids or lithium salts|

---

CN110172031B|2019-05-23|2021-03-16|北京师范大学|Anionic N-substituted aniline ionic liquid and preparation method thereof|

法律状态:
2017-06-22| PLFP| Fee payment|Year of fee payment: 2 |

---

2017-12-15| PLSC| Search report ready|Effective date: 20171215 |

---

2018-06-18| PLFP| Fee payment|Year of fee payment: 3 |

---

2020-06-30| PLFP| Fee payment|Year of fee payment: 5 |

---

2021-06-30| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

---

申请号 | 申请日 | 专利标题

---

FR1655373A|FR3052598B1|2016-06-10|2016-06-10|USE OF IONIC LIQUIDS AS ADJUVANT IN ELECTROCHEMISTRY|

---

FR1655373|2016-06-10|FR1655373A| FR3052598B1|2016-06-10|2016-06-10|USE OF IONIC LIQUIDS AS ADJUVANT IN ELECTROCHEMISTRY|

---

PCT/FR2017/051453| WO2017212179A1|2016-06-10|2017-06-08|Use of ionic liquids as an adjuvant in electrochemistry|

---

EP17733510.6A| EP3469647A1|2016-06-10|2017-06-08|Use of ionic liquids as an adjuvant in electrochemistry|

---

JP2018564772A| JP2019520677A|2016-06-10|2017-06-08|Use of ionic liquids as adjuvants in electrochemistry|

---

US16/306,943| US20190148754A1|2016-06-10|2017-06-08|Use of ionic liquids as an adjuvant in electrochemistry|

---

CN201780035957.1A| CN109643817A|2016-06-10|2017-06-08|Ionic liquid is in electrochemistry as the purposes of adjuvant|

---

CA3025139A| CA3025139A1|2016-06-10|2017-06-08|Use of ionic liquids as an adjuvant in electrochemistry|