WO2018144480A1 - Procédé de production d'une solution électrolytique de sel métallique alcalin hygroscopique - Google Patents

Procédé de production d'une solution électrolytique de sel métallique alcalin hygroscopique Download PDF

Info

Publication number
WO2018144480A1
WO2018144480A1 PCT/US2018/016015 US2018016015W WO2018144480A1 WO 2018144480 A1 WO2018144480 A1 WO 2018144480A1 US 2018016015 W US2018016015 W US 2018016015W WO 2018144480 A1 WO2018144480 A1 WO 2018144480A1
Authority
WO
WIPO (PCT)
Prior art keywords
solvent
solution
water
alkali metal
electrolyte
Prior art date
Application number
PCT/US2018/016015
Other languages
English (en)
Inventor
Joseph Carl POSHUSTA
Jerry Lynn MARTIN
Original Assignee
Synthio Chemicals, LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Synthio Chemicals, LLC filed Critical Synthio Chemicals, LLC
Priority to EP18748078.5A priority Critical patent/EP3577710A4/fr
Priority to CN201880023167.6A priority patent/CN110870125A/zh
Priority to KR1020197025560A priority patent/KR20190110608A/ko
Publication of WO2018144480A1 publication Critical patent/WO2018144480A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the production of low-water-content electrolyte solutions in general. It is particularly applicable to the production of low-water-content electrolytes compromising alkali (e.g., lithium, sodium, potassium, or a combination thereof) salts and non-aqueous solvents for use in alkali metal or alkali-ion (e.g., lithium- or lithium-ion) batteries.
  • alkali e.g., lithium, sodium, potassium, or a combination thereof
  • non-aqueous solvents for use in alkali metal or alkali-ion (e.g., lithium- or lithium-ion) batteries.
  • Electrolytes for lithium- and lithium-ion batteries typically require nonaqueous electrolytes with low water content in order to obtain acceptable calendar and cycle life.
  • Commercial electrolytes for lithium-ion batteries typically specify water contents of no more than 500 parts per million (ppm) by weight, typically no more than 400 ppm, often no more than 300 ppm, still more often no more than 200 ppm, yet still more often no more than 100 ppm, and most often below 50 ppm by weight.
  • These electrolytes typically comprise one or more non-aqueous or aprotic solvents and one or more lithium salts, such as lithium hexafluorophosphate (LiPF 6 ).
  • a common electrolyte production method includes removing the water from a solvent mixture and then mixing in a lithium salt powder. It is difficult and expensive to remove water from the electrolyte once the lithium salt is combined with the solvent, so the lithium salt added to the electrolyte must have very low water content, typically less than 100 ppm.
  • LiFSI lithium bis(fluorosulfonyl)- imide
  • LiPF 6 salts provide higher conductivity solutions, and are more stable against hydrolysis, which improves battery lifetime and performance at elevated temperatures.
  • NaFSI salts have also been reported for sodium-ion batteries, and KFSI is a candidate for use in both potassium and sodium-ion batteries.
  • Production of dry, free-flowing alkali metal salts of bis(fluorosulfonyl)imide with low water content is technically challenging.
  • LiFSI is deliquescent (i.e., it can absorb enough water vapor from the air to form a liquid solution), and therefore all handling is typically performed in closed systems or dry rooms with very low humidity.
  • LiFSI/water mixtures are not stable at high temperatures, for example, 50% LiFSI/water mixtures can decompose violently above 120 °C. More importantly, concentrated
  • LiFSI/water mixtures can form complexes with extremely low vapor pressure. Hydrolysis of the LiFSI salt proceeds rapidly at temperatures above 60 °C, so it is not practical to heat water-containing LiFSI powder or solutions to higher temperatures in order to speed the water removal. This makes final removal of water from LiFSI powders complex and expensive.
  • Prior art methods for drying LiFSI salts include vacuum drying, anti-solvent precipitation, and water vapor stripping with dry gas.
  • LiFSI While heating the concentrated solution would theoretically raise the solvent vapor pressure, LiFSI will quickly consume water by hydrolysis at elevated temperatures and generate acids of fluoride, sulfate, and sulfamate, which are undesirable in LiFSI electrolytes.
  • Most prior art processes for producing dry lithium salts require the use of volatile organic solvents. If these solvents are not components of the final electrolyte, they must be removed from the salt before final electrolyte blending. Removal of these solvents is time consuming, expensive, and presents both safety concerns from the handling of flammable solvents and environmental hazards due to potential release of volatile organic compounds into the environment.
  • Some aspects of the invention overcome prior obstacles to the production of dry (low water content), high purity electrolyte solutions comprising lithium salts and nonaqueous solvents.
  • Methods of the invention provide a process for producing electrolyte solutions with low water content in a cost-effective and safe manner, with reduced solvent use and increased yield.
  • One particular aspect of the invention provides a method for producing an aprotic electrolyte solution comprising a hygroscopic alkali metal salt.
  • the method generally includes admixing the following components: (i) a liquid solution comprising an acidic form of said hygroscopic alkali metal salt and a first solvent, (ii) an alkali metal base, and (iii) an aprotic electrolyte solvent.
  • the resulting mixture produces a vapor which includes water, a first solvent or a combination thereof.
  • the vapor is then removed from the mixture to reduce the amount of water to produce the aprotic electrolyte solution.
  • the resulting electrolyte solution typically contains no more than 500 parts per million (ppm) of water by weight, typically no more than 400 ppm, often no more than 300 ppm, still more often no more than 200 ppm, yet still more often no more than 100 ppm, and most often below 50 ppm.
  • ppm parts per million
  • the method includes adding the electrolyte solvent to the mixture to maintain the concentration of the alkali metal electrolyte below the concentration where the vapor pressure of the resulting solution mixture is more than one-tenth of the product of the vapor pressure of the pure aprotic electrolyte solvent and its mole fraction in the solution mixture.
  • Another aspect of the invention provides a simplified method for producing secondary battery electrolytes without the need to isolate a dry alkali metal salt.
  • the present invention provides simpler, less expensive, and high-yield process for electrolyte production.
  • the method of the invention reduces the cost and complexity of electrolyte production, as pumping and mixing liquid solutions utilizes simpler and less expensive equipment than that required to handle dry powders.
  • Still another aspect of the invention provides a simple and cost-effective process for removing water from solvent/salt solutions, thereby enabling the use of liquid acid precursors to lithium salts such as HFSI and hydrogen bis(trifluoromethylsulfonyl)imide (HTFSI).
  • liquid acid precursors such as HFSI and hydrogen bis(trifluoromethylsulfonyl)imide (HTFSI).
  • HTFSI hydrogen bis(trifluoromethylsulfonyl)imide
  • the invention also provides a method for producing high-purity LiFSI dry powder.
  • a method for producing high-purity LiFSI dry powder includes producing a low-water content electrolyte solution comprising LiFSI as described herein. Thereafter, the LiFSI can be precipitated from the solution using a low-polarity anti-solvent (i.e., precipitation solvent) such as hexane, dichloromethane or toluene.
  • a low-polarity anti-solvent i.e., precipitation solvent
  • the water removal step can be accomplished efficiently using the methods described herein, and then various methods known to those skilled in the art can be used to either remove the solvent or precipitate the LiFSI from the solution.
  • the invention also includes a method for producing a non-aqueous electrolyte solution comprising LiFSI, NaFSI, KFSI or a combination thereof.
  • the invention also provides dry salts thereof, which can be produced using the methods disclosed herein.
  • Such non-aqueous electrolyte solutions are useful in batteries, including lithium, sodium and/or potassium batteries.
  • the invention also provides a process for producing a low-water-content alkali metal electrolyte solution from the corresponding acidic electrolyte material such as HFSI and hydrogen bis(trifluoromethylsulfonyl)imide (HTFSI).
  • the process of the invention includes contacting metal carbonates or metal hydroxides with the acidic electrolyte material in the presence of suitable battery solvents.
  • the process can also include removing the water without isolating the metal salt of the electrolyte material.
  • the methods disclosed here eliminate process steps (e.g., isolation of solid metal electrolyte material), require smaller and less complex equipment, and provide higher yield.
  • Methods of the invention are particularly useful for providing a low water content solution of a compound of the formula:
  • M 1 is an alkali metal (such as sodium, potassium, lithium, rubidium, cesium, or francium), and each of R 1 and R 2 is independently selected from the group consisting of fluoride and a fluorinated C 1-6 alkyl.
  • Figure 1 is a schematic illustration of one particular embodiment of the invention for removing water from LiFSI/solvent solutions.
  • Figure 2 is a schematic illustration of yet another embodiment of the invention for removing water from LiFSI/solvent solutions with solvent recycling.
  • FIG. 3 is a schematic illustration of still yet another embodiment of the invention for continuous removal of water from LiFSI/solvent solutions with solvent recycling.
  • FIG. 4 is a schematic illustration of a particular embodiment of the invention for producing a low water content LiFSI solution from HFSI.
  • concentrations are on a weight basis; i.e. 50 ppm means 50 parts by weight out of 1,000,000 parts and 50% means 50% by weight.
  • the terms "low water content,” “free of water,” “anhydrous,” “water free,” “dry organic solvent (or solution),” “dry solvent (or solution),” and “non-aqueous solvent (or solution)” are used interchangeably herein and refer to a composition having water content of about 1,000 ppm or less, typically about 500 ppm or less, often 250 ppm or less, more often about 100 ppm or less, and most often about 50 ppm or less.
  • the nonaqueous solvent is an aprotic solvent.
  • aprotic when referring to a solvent or a solution means the amount of protic solvent present is about 1,000 ppm or less, typically about 500 ppm or less, often 250 ppm or less, more often about 100 ppm or less, and most often about 50 ppm or less.
  • the term “about” when referring to a numeric value refers to ⁇ 20%, typically ⁇ 10%, often ⁇ 5% and more often ⁇ 2% of the numeric value.
  • electrolyte refers to a chemical compound (typically a salt) that conducts electricity by changing into ions when melted or dissolved into a solution.
  • An example of an electrolyte is sodium chloride and a compound of Formula I.
  • electrolyte solution refers to a mixture of an electrolyte, solvent and optionally additives that can be used as a battery.
  • “removal of water” means the resulting solution has water content of about 1,000 ppm or less, typically about 500 ppm or less, often about 300 ppm or less, more often about 100 ppm or less, and most often about 50 ppm or less.
  • the term “removal of water” means reducing the water content by at least about 50%, typically at least about 70%, often at least about 80%, often at least 90%, and more often at least 95% from the starting liquid solution.
  • the Sato '780 Patent states "A difficulty of removal of the reaction solvent from the reaction solution because of a significant interaction between the alkali metal salt of fluorosulfonyl imide and the solvent occurs after a time a time point at which the amount of the reaction solvent is 150% by mass or less based on [the mass] of the alkali metal salt of fluorosulfonyl imide.”
  • the inventors have found that water vapor can be removed from dilute solutions more than 100 times faster than with prior art methods using the process disclosed herein. This two-order-of-magnitude increase in the drying rate for a 10% change in solvent concentration is surprising and unexpected.
  • the process of the invention has significantly higher yield of compound of Formula I (e.g., LiFSI) than conventional processes, approaching 100% yield.
  • This increase in yield is of high commercial value, and has not been obtained in prior art processes, despite intense research and development by multiple groups worldwide.
  • One particular aspect of the invention provides a method for producing a nonaqueous electrolyte solution comprising a hygroscopic alkali metal salt electrolyte (e.g., a compound of Formula I).
  • a method for producing a nonaqueous electrolyte solution comprising a hygroscopic alkali metal salt electrolyte (e.g., a compound of Formula I).
  • a hygroscopic alkali metal salt electrolyte e.g., a compound of Formula I
  • the non-aqueous solvent is selected from the group consisting of an acyclic carbonate, a cyclic carbonate, an acyclic ether, a cyclic ether, an ionic liquid, water and a mixture thereof. Still in other embodiments, the method further includes the step of adding additional amount of the non-aqueous solvent to the non-aqueous electrolyte solution produced in the step (b) and repeating the step (b). The additional amount of non-aqueous solvent can be added continuously or batch-wise.
  • the non-aqueous solvent can be recovered from the vapor and reused.
  • Recovery of the non-aqueous solvent from the vapor includes removing water from the vapor to produce a low-water content non-aqueous solvent.
  • Recovery can also include condensing the vapor prior to or after removing water.
  • Water can be removed from the vapor (prior to and/or after condensation of the vapor) using any of the methods known to one skilled in the art including, but not limited to, phase separation, distillation, adsorption, extraction, membrane separation, chemical reaction, and a combination thereof.
  • the method of the invention is used to produce the non-aqueous electrolyte solution having no more than 1000 ppm, typically about 500 ppm or less, often 250 ppm or less, more often about 100 ppm or less, and most often about 50 ppm or less of water by weight.
  • the amount of non-aqueous electrolyte solvent added to the admixture is sufficient to maintain the hygroscopic alkali metal salt concentration below the concentration where the vapor pressure of the resulting solution mixture is more than one- tenth of the product of the vapor pressure of the pure non-aqueous electrolyte solvent and its mole fraction in the solution mixture.
  • the concentration of the alkali metal salt electrolyte is maintained such that the resulting vapor pressure is near or consistent with that predicted by Raoult's law, i.e., within about ⁇ 25%, typically within about ⁇ 10%, and often within about ⁇ 5 %.
  • Raoult's law states that the partial vapor pressure of each component of an ideal mixture of liquids is equal to the vapor pressure of the pure component multiplied by its mole fraction in the mixture.
  • Raoult's law states the relative lowering of vapor pressure of a dilute solution containing nonvolatile solute is equal to the mole fraction of solute in the solution.
  • Typical alkali metal bases include alkali metal carbonate, alkali metal hydroxide, alkali metal bicarbonate, or a combination thereof.
  • Another aspect of the invention provides a method for producing a nonaqueous electrolyte solution comprising a hygroscopic alkali metal salt and about 1000 ppm or less of water.
  • a method for producing a nonaqueous electrolyte solution comprising a hygroscopic alkali metal salt and about 1000 ppm or less of water.
  • Such a method includes:
  • step (c) adding an additional amount of said non-aqueous electrolyte solvent to said electrolyte solution produced in said step (b), wherein the amount of said non- aqueous-electrolyte solvent added is sufficient to maintain said alkali metal electrolyte concentration below the concentration where the vapor pressure of said admixture solution is more than one-tenth of the product of the vapor pressure of the pure non-aqueous electrolyte solvent and its mole fraction in said admixture solution;
  • the non-aqueous electrolyte solvent that is used has a low water content.
  • the water content of the non-aqueous electrolyte solvent used is about 1,000 ppm or less, often about 500 ppm or less, more often about 250 ppm or less, and most often about 100 ppm or less.
  • the electrolyte solvent can be recovered from the vapor and reused as described above.
  • the additional amount of the non-aqueous electrolyte solvent added in the step (c) can include at least a portion of the recovered electrolyte solvent.
  • Steps (b)-(d) can be a continuous process or one or more steps can be conducted in a batch-wise process.
  • temperature of the solution is maintained at about 50 °C or less, often at about 40 °C or less throughout the entire process.
  • the vapor is removed from the admixture solution at a pressure between 0.01 torr and about 500 torr.
  • the vapor is removed from the admixture solution at temperature between about 10 °C and about 80 °C.
  • the hygroscopic alkali metal electrolyte salt (e.g., compound of Formula I) is lithium bis(fluorosulfonyl)imide (“LiFSI").
  • one specific embodiment of the invention provides a method for producing an aprotic electrolyte solution comprising lithium bis(fluorosulfonyl)-imide (“LiFSI").
  • LiFSI lithium bis(fluorosulfonyl)-imide
  • Exemplary aprotic solvents used in such a method include, but are not limited to, diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), acetonitrile, methanol, ethanol, and a mixture thereof.
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • EC ethylene carbonate
  • acetonitrile methanol
  • ethanol ethanol
  • aprotic solvents used in such a method include, but are not limited to, diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), acetonitrile, methanol, ethanol, and a mixture thereof.
  • EMC ethylmethyl carbonate
  • EC ethylene carbonate
  • acetonitrile acetonitrile
  • methanol ethanol
  • ethanol acetonitrile
  • methanol ethanol
  • ethanol ethanol
  • a non-aqueous electrolyte solution comprising one or more alkali metal salts (e.g., compound of Formula I) and a non-aqueous solvent with low water content.
  • Water is removed from a solution of organic solvents, alkali salts and water while maintaining the salt concentration below a critical value.
  • the process can be conducted at temperatures that do not result in excessive degradation of the alkali metal salt.
  • Methods and the processes of the invention can be used to produce provide electrolyte solutions having the water content of about 1000 ppm or less by weight, typically about 500 ppm or less, often about 400 ppm or less, more often about 300 ppm or less, still more often about 200 ppm or less, yet more often about 100 ppm or less, and most often about 50 ppm or less.
  • the invention also provides a method for producing non-aqueous electrolyte solutions by combining a low-water-content electrolyte solution with other electrolyte component(s) such as a compound of Formula I, co-solvent(s) and/or additive(s) to yield an electrolyte solution suitable for use in non-aqueous batteries. Electrolyte solutions produced by this method provide batteries with improved performance and lifetime.
  • the electrolyte solution of the invention comprises a metal salt that is used in batteries as an electrolyte.
  • the metal salt is a hygroscopic metal salt, e.g., a compound of Formula I.
  • hygroscopic means ability of a dry metal salt (i.e., having about 1000 ppm or less, typically about 500 ppm or less and often about 100 ppm or less water content) to attract (e.g., absorb and/or adsorb) water molecules from atmosphere at standard conditions (e.g., at room temperature (20 °C) at 1 atmospheric pressure).
  • Suitable metal salts include hygroscopic metal salts that are known to one skilled in the art for use in batteries or in electrolyte solutions.
  • the metal salt is a compound of Formula I.
  • the metal salt is a lithium metal salt.
  • the metal salt is LiFSI.
  • Organic solvents that can be used in the invention include any organic solvent known to one skilled in the art. Either protic or aprotic solvents can be used. In one particular embodiment, organic solvent is an aprotic solvent. Exemplary aprotic organic solvents that can be used in the invention include, but are not limited to, cyclic- and acyclic carbonates and esters.
  • Suitable aprotic organic solvents include, but are not limited to, acetonitrile, ⁇ -butyrolactone, diethyl carbonate, 1,2-dimethoxy ethane, dimethyl carbonate, 1,3-dioxolane, ethyl acetate, ethylene carbonate, ethyl methyl carbonate, propylene carbonate, tetrahydrofuran, methyl propionate, fluorinated carbonates, and the like.
  • the solvent that is used in the electrolyte solution of the invention comprises a mixture of two or more organic solvents and can also include one or more ionic liquids.
  • the electrolyte solution of the invention is a lithium ion battery electrolyte solution.
  • solvents for a lithium ion battery electrolyte can include the same non-aqueous solvent used in the drying process.
  • the need to completely e.g., about 90% or more, typically about 95% or more, often about 98% or more, and more often about 99% or more
  • remove the non-aqueous solvent from the metal salt in the drying process before producing the final electrolyte can be eliminated, resulting in reduced process complexity and improved process yield.
  • the inventive method can be applied to other alkali metal salts, including sodium, lithium, potassium, rubidium, cesium and francium salts, and a mixture thereof.
  • alkali metal salts including sodium, lithium, potassium, rubidium, cesium and francium salts, and a mixture thereof.
  • the present invention is described herein in reference to removing water from lithium metal salts.
  • the present invention will now be described in reference to removing water from a solution comprising LiFSI.
  • the process of the invention provides removing water from a first non-aqueous solvent and LiFSI, while maintaining the concentration of the salt in a range where the vapor pressure of the mixture exceeds 0.1 torr at 50 °C.
  • the method can remove water to well below 100 ppm and without heating to temperatures that can lead to significant decomposition or hydrolysis of the LiFSI (e.g., about 10% or less, typically about 5% or less and often about 1% or less decomposition or hydrolysis).
  • One particular process of the invention is schematically illustrated in Figure 1.
  • the process removes water by adding dry solvent (e.g., a second non-aqueous solvent) to a starting liquid phase LiFSI/solvent (e.g., a first non-aqueous solvent)/water mixture and then removing the first non-aqueous solvent and water as a vapor.
  • the first non-aqueous solvent vapor carries at least a portion of water vapor out of the solution.
  • the second non-aqueous solvent can be fed to the process as either a liquid or a vapor, but in either case it is mixed with the starting LiFSI/solvent/water solution.
  • LiFSI/solvent refers to a first nonaqueous solvent, i.e., a solvent in which drying is desired.
  • Dry solvent can be any solvent that is compatible with LiFSI and water.
  • LiFSI is soluble in the dry solvent (e.g., second non-aqueous solvent) that is used in the drying process.
  • the dry solvent has a pure-component (at standard conditions, e.g., room temperature at 1 atmospheric pressure) vapor pressure of between 0.1 and about 760 torr, typically between 1 and about 50 torr, and often between 1 and about 17.5 torr.
  • the mole ratio of LiFSI to solvent is adjusted to provide a solution vapor pressure between 0.1 and about 760 torr at between 0 °C and 80 °C, typically between 1 and about 300 torr at between 10 °C and 60 °C, and often between 1 and about 50 torr at between 20 °C and 50 °C.
  • Suitable solvents include, but are not limited to, polar solvents such as alcohols, acetates, nitriles, formamides, carbonates, ethers, nitrates, and amines.
  • Specific exemplary solvents include ethanol, ethyl acetate, acetonitrile, formamide, diethyl carbonate, diethyl ether, ethyl methyl carbonate, nitromethane, and butyl amine.
  • mixtures of solvents can be used, as long as the mixture exhibits the required vapor pressure.
  • the solvent is an acyclic carbonate (such as, but not limited to, diethyl carbonate and ethylmethylcarbonate), a cyclic carbonate (such as, but not limited to, propylene carbonate and ethylene carbonate), an acyclic ether (such as, but not limited to, 1,2-dimethoxy ethane), a cyclic ether (such as, but not limited to, dioxolane and 1,4-dioxane), an ionic liquid (such as, but not limited to, l-ethyl-3-methylimidazolium bis(fluorosulfonyl)-imide and 1 -methyl- 1-propylpyrrolidiunium
  • acyclic carbonate such as, but not limited to, diethyl carbonate and ethylmethylcarbonate
  • a cyclic carbonate such as, but not limited to, propylene carbonate and ethylene carbonate
  • an acyclic ether such as, but not limited to
  • the remaining dry solvent can be removed by any method known to those skilled in the art. Such methods include solvent stripping with dry gas, heating at atmospheric pressure or heating under a vacuum. Combinations of these methods can be used. Alternatively, a dry LiFSI powder can be produced by adding a low-polarity anti-solvent such as toluene or
  • the term "anti-solvent" refers to a solvent that can be used to precipitate LiFSI particles from a solution.
  • Particularly useful solvents are those that comprise at least part of the final electrolyte mixture.
  • diethyl carbonate is a component in some commercial lithium-ion battery electrolytes.
  • the step of removing the drying solvent or precipitating the lithium salt can be eliminated, resulting in further simplification of the process.
  • the evaporated solvent is recovered and recycled.
  • This embodiment of the invention is schematically illustrated in Figure 2.
  • the drying process can be either a separate batch process where a sufficient amount of the second dry solvent is added to a batch of LiFSI/solvent, or a continuous process that recovers the evaporated solvent and dries the recovered solvent vapor before recycling, i.e., returning it to the LiFSI/solvent solution.
  • the first non-aqueous solvent can be the same as the second non-aqueous solvent.
  • the second non-aqueous solvent is a dry solvent whereas the first non-aqueous solvent/salt mixture contains water.
  • Drying the recovered second non-aqueous solvent can be achieved either in the liquid or vapor phase.
  • a convenient means for recovering the second non-aqueous solvent is to condense the second non-aqueous solvent vapor and remove the water from the condensate, after which the recovered second non-aqueous solvent is ready to be recycled into the LiFSI/solvent drying process. Drying the recovered second non-aqueous solvent in the liquid phase can include phase separation (for solvents with low water miscibility), physical adsorption, chemical conversion or a combination of these processes.
  • Suitable physical adsorbents that can be used to dry second non-aqueous solvent include, but are not limited to, molecular sieves, alumina and other desiccants known to those skilled in the art.
  • Exemplary chemical conversion includes reaction with thionyl chloride or calcium hydride.
  • Vapor phase drying of recovered second non-aqueous solvent can also include physical adsorbents and/or chemical reaction. Other solvent drying methods known to those skilled in the art can also be used, such as distillation.
  • One particular advantage of the process of the invention is that drying recovered second non-aqueous solvent occurs separately from drying the mixture of
  • LiFSI/solvent In the second non-aqueous solvent drying step, no metal salt is present, thereby enabling the use of low-cost, widely available molecular sieves and zeolites as desiccants. Most common zeolites include alkali metals other than lithium. Attempts to dry lithium salts/solvent solutions using these zeolites often results in cation exchange between the salt and the zeolite, leading to both contamination of the electrolyte with non-lithium alkali metals like sodium or potassium, and loss of lithium from the electrolyte mixture. These problems can be avoided using lithium-exchanged zeolites, but the use of lithium- exchanged zeolites for bulk water removal is not cost-effective.
  • FIG. 3 shows continuous removal of water from a stream of LiFSI/solvent/water solution that incorporates a continuous solvent drying process for recycling the solvent used for water removal.
  • the contact between the dry solvent and the LiFSI/solvent/water solution can be conducted in stages to achieve sufficient removal of water. In one particular embodiment of the invention, these stages are conducted in a counter- flow staged separator such as a packed column or tray column.
  • the wet LiFSI/solvent solution is fed to the top of a packed column, and dry solvent vapor is fed to the bottom of the column.
  • the packing provides good interphase contact between the solution and the solvent vapor passing upwards through the column. In this manner, the water is stripped from the solution and exits the top of the column and the dried LiFSI/solvent solution exits the bottom of the column.
  • the vapor pressure of the LiFSI/solvent solution at low water concentrations can be approximated by the ideal Raoult's law where the vapor pressure of the solvent in the solution is equal to the product of the solvent mole fraction and its pure component vapor pressure.
  • Raoult's law agreed well when the lithium-salt-to-solvent molar ratio is below about 0.3.
  • the measured solution vapor pressure dropped several times below that predicted from Raoult's law.
  • the inventors here have found that maintaining a LiFSI/solvent solution vapor pressure near that predicted by Raoult's law enables vaporization of the solvent and water from the solution and subsequent drying by the method described in this invention under practical conditions. If the salt concentration is too high, the solution vapor pressure drops below practical conditions under which the invention may be practiced.
  • certain aspects of the invention can be used to produce dry LiFSI powder.
  • the target value e.g., about 500 ppm or less, typically about 200 ppm or less and often about 100 ppm or less
  • salt powder can be produced from the dry salt/solvent mixture.
  • a number of methods for producing dry powder from such solutions are known to those skilled in the art.
  • One class of such methods involves evaporating the solvent though various combinations of contacting with a dry gas, heating and exposing to vacuum. These may be practical once the water is removed, because the solution can be heated to higher temperatures without causing degradation of the lithium salt due to interaction with water.
  • Another embodiment of the invention includes adding a liquid which is a poor solubility solvent (an "anti-solvent") for the hygroscopic metal salt (e.g., lithium salt) to the salt/solvent mixture so as to cause the salt to precipitate.
  • an anti-solvent refers to a solvent in which the hygroscopic metal salt has a solubility of about 50 g/L or less, typically about 10 g/L or less, and often 1 g/L or less.
  • Yet another aspect of the invention provides a method for producing an aprotic electrolyte solution comprising a hygroscopic alkali metal salt.
  • the method includes admixing (i) a liquid solution comprising an acidic form of the hygroscopic alkali metal salt (e.g., a compound of Formula I) in a first solvent, (ii) an alkali metal base, and (iii) an aprotic electrolyte solvent. See Figure 4.
  • the admixture is subjected to conditions sufficient to produce a solution mixture where the solution mixture comprises (i) a vapor comprising water, a first solvent or a combination thereof, and (ii) the hygroscopic alkali metal salt.
  • the method also includes a step of removing the vapor from the solution mixture thereby reducing the amount of water in the solution mixture to produce the desired aprotic electrolyte solution.
  • this particular method produces the alkali metal in situ by reacting the acidic form of the electrolyte with an alkali metal base.
  • Suitable alkali metal base include hydroxides, carbonates, and bicarbonates.
  • the resulting reaction produces water and/or carbon dioxide as by products which are removed during the step of removing the vapor.
  • the method of the invention avoids having to dry the alkali metal salt of the electrolyte, which is a typical required in conventional methods.
  • Another aspect of the invention provides a method for producing an electrolyte solution from a liquid solution comprising a mixture of a hygroscopic alkali metal electrolyte, an organic solvent and water.
  • the method generally includes combining (i) an electrolyte solvent having water content of about 100 ppm or less and (ii) a liquid solution under conditions sufficient to produce an admixture solution and a vapor comprising the organic solvent and water. The vapor is then removed to reduce the amount of the organic solvent (which is typically used in production and/or isolation of the electrolyte) and water from the admixture solution to produce the electrolyte solution having no more than 500 ppm of water by weight.
  • the electrolyte solvent is added such as to maintain the alkali metal electrolyte concentration below the concentration where the vapor pressure of the admixture solution is more than one-tenth of the product of the vapor pressure of the pure electrolyte solvent and its mole fraction in the admixture solution.
  • the electrolyte solvent is added such as to maintain the alkali metal electrolyte concentration below the concentration where the vapor pressure of the admixture solution is more than one-tenth of the product of the vapor pressure of the pure electrolyte solvent and its mole fraction in the admixture solution.
  • Example 1 A wet solution of LiFSI and diethyl carbonate (DEC) was prepared by mixing 100 g of DEC, 54.6 g LiFSI, and 1.59 g water. The solution was found to have 1.0 wt% water from Karl Fischer titration. This solution was placed in a 1 L three-neck round bottom flask with a magnetic stir bar and a heating mantle. One flask neck was closed with a ported stopper through which a thermocouple was immersed in the LiF SI/DEC solution. Another neck was fitted with a 125 mL pressure equalizing addition funnel filled with 117.5 g DEC having 130 ppm w water as measured by Karl Fischer titration.
  • DEC diethyl carbonate
  • the final neck was fitted with a vacuum port Liebig distillation head.
  • a I L round bottom flask was attached to the receiving end of the distillation head. This receiving flask was immersed in an ice bath.
  • the distillation condenser was cooled to -5 °C with an external chiller.
  • a diaphragm vacuum pump was connected to the vacuum port of the distillation head and the pressure was reduced to about 15 torr.
  • the LiFSI/DEC solution was heated to 37 °C under constant power from the external heating mantle at which point the solution began to boil and condensate was observed in the receiving flask. The boiling temperature was maintained by slow addition of DEC from the addition funnel.
  • the addition funnel was emptied, the heating was stopped, the vacuum relieved, and the LiFSI/DEC solution was sampled and found to have 2400 ppm w water.
  • the addition funnel was filled with 118.0 g DEC, the vacuum was set to about 15 torr and the heater power was applied, and DEC was added to the LiFSI/DEC solution to maintain boiling at about 37 °C.
  • the LiFSI/DEC solution was again sampled and found to have 550 ppm w water.
  • the addition funnel was filled a third time with 107.7 g DEC and the drying process was restarted.
  • the final water content in the LiFSI/DEC solution was found to be 190 ppm w .
  • the receiving flask was found to contain 324.1 g DEC including some water droplets visible at the bottom of the flask.
  • the three-neck flask contained 166.6 g LiFSI/DEC solution.
  • Example 2 A wet solution of LiFSI and ethyl methyl carbonate (EMC) was prepared by mixing 47.2 g LiFSI, 88.6 g EMC and 1.432 g water. The solution was found to have 1.06 wt% water by Karl Fischer titration. 123.0 g of this solution was placed in a 300 mL three-neck round bottom flask with a magnetic stir bar and a heating mantle. The flask was connected to the apparatus described in Example 1. The LiFSI/EMC solution was heated to about 42 °C under constant power from the heating mantle. Vacuum was applied at about 30 torr and the condenser was cooled to about -6 °C.
  • EMC ethyl methyl carbonate
  • Dry EMC was added to the LiFSI/EMC solution from the addition funnel and boiling was observed with condensate collection in the receiving funnel. After the contents of the addition funnel was added, the water content of the LiFSI/EMC solution was measured by Karl Fischer titration and the addition funnel was refilled with dry EMC. Table 1 shows the amount of EMC added and the resulting water concentration in the LiFSI/EMC solution after each of these additions.
  • the condensed EMC in the receiving flask was a single phase with a total mass of 738.1 g.
  • the water content of the EMC condensate was 1680 ppm as measured by Karl Fischer titration.
  • Comparative example 1 A solution of LiFSI in EC was dried by flowing through a packed column operated at reduced pressure. LiFSI/EC solution with water was fed to the top of a packed column while dry argon gas was fed to the bottom of the column. Approximately 500 grams of solution with an initial concentration of 49% LiFSI, 49% EC and 2% water was passed through the column. Water content in the exit solution was measured using Karl Fischer titration. After passing through the column, the dried solution was returned to the top of the column for additional passes. Nine passes through the column were required to reduce the water content from 10,000 ppm to 2000 ppm. The water removal rate decreased asymptotically for each pass, which severely limits the practicality of this approach. Each pass took more than 30 minutes, for a total of 4.5 hours. Compared to Example 1, this method showed a significantly slower drying rate.
  • Example 3 A solution of LiFSI in water was prepared by mixing HFSI with lithium carbonate. In a jacketed flask equipped with a mechanical stirrer, 814 grams of water was added with 747 grams of lithium carbonate. 3700 g of HFSI was added dropwise to the reactor over the course of 3.5 hours, while maintaining the reactor temperature below 20 °C by circulating coolant through the jacket. After completing the addition of the HFSI, the reactor contents were drained and filtered, yielding an aqueous solution containing 78% LiFSI by mass. This solution was then mixed with DEC and dried using the methods of Example 1.
  • Process effluents were C0 2 , water and a minor solid impurity stream
  • LiFSI salt solution between 20% and 30% by mass was obtained. It should be noted higher concentrations can also be obtained.
  • Example 4 shows a method of drying where a hydrophobic solvent is dried by condensing the vapor and recycling the dry solvent.
  • a LiFSI/H 2 0 solution was prepared by neutralizing 1099.6g HFSI in a slurry of 224.3 g Li 2 C0 in 201 g H 2 0 to yield a 77.4 wt% LiFSI solution. The solution was filtered to remove minor solid byproducts. Then, 408.4g of the filtered solution and 924. Og diethylcarbonate were added to a 2L multi- neck round bottom flask with a magnetic stir bar, a thermometer, and a 5 -inch vigreaux distillation column.
  • the column was a condenser and a receiving vessel that allowed phase separation of the condensate and return of the dry solvent to the top of the distillation column.
  • the head space of the condenser was connected to a diaphragm vacuum pump.
  • the condenser was cooled to about 0 °C, and the receiving vessel was immersed in a water/ice bath.
  • the flask was heated at constant power with a heating mantle, the pressure was reduced to about 6 to 15 torr, and the solution was boiled at between about 28 and 37 °C with periodic draining of water from the receiving vessel. After 7 hours the water content of the solution in the flask was 65 ppm by Karl Fisher titration.
  • the solution was filtered and returned to the apparatus and distilled under the column and condenser for another 2.5 hours and the water content was 24 ppm.
  • a larger receiving vessel was placed on the condenser and 304.7g excess diethylcarbonate was removed from the solution.
  • 756.5g of LiFSI/diethylcarbonate solution was recovered having a water content of 21 ppm, and a LiFSI concentration of 42 wt%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un procédé de production de solutions électrolytiques à faible teneur en eau. En particulier, la présente invention concerne un procédé d'élimination de l'eau d'une solution liquide comprenant un solvant non aqueux, un sel métallique hygroscopique et de l'eau. L'invention concerne également un procédé de production d'une solution électrolytique à faible teneur en eau sans isolement du sel métallique. Le procédé de l'invention est utile dans la production de solutions électrolytiques à faible teneur en eau pour des batteries telles que des batteries au lithium ou au lithium-ion.
PCT/US2018/016015 2017-01-31 2018-01-30 Procédé de production d'une solution électrolytique de sel métallique alcalin hygroscopique WO2018144480A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP18748078.5A EP3577710A4 (fr) 2017-01-31 2018-01-30 Procédé de production d'une solution électrolytique de sel métallique alcalin hygroscopique
CN201880023167.6A CN110870125A (zh) 2017-01-31 2018-01-30 制备吸湿性碱金属盐电解质溶液的方法
KR1020197025560A KR20190110608A (ko) 2017-01-31 2018-01-30 흡습성 알칼리 금속염 전해질 용액 생산 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762452931P 2017-01-31 2017-01-31
US62/452,931 2017-01-31

Publications (1)

Publication Number Publication Date
WO2018144480A1 true WO2018144480A1 (fr) 2018-08-09

Family

ID=63041069

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/016015 WO2018144480A1 (fr) 2017-01-31 2018-01-30 Procédé de production d'une solution électrolytique de sel métallique alcalin hygroscopique

Country Status (4)

Country Link
EP (1) EP3577710A4 (fr)
KR (1) KR20190110608A (fr)
CN (1) CN110870125A (fr)
WO (1) WO2018144480A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109734061A (zh) * 2019-02-14 2019-05-10 湖南福邦新材料有限公司 一种双氟磺酰亚胺锂的制备方法
CN109742455A (zh) * 2018-12-24 2019-05-10 深圳市量能科技有限公司 一种锂离子电池的制作方法
CN115335543A (zh) * 2020-03-06 2022-11-11 内华达高等教育系统董事会代表拉斯维加斯内华达大学 从溶解在离子液体中的锂盐回收锂
WO2023276812A1 (fr) 2021-06-30 2023-01-05 株式会社日本触媒 Procédé de production de composition et solution électrolytique non aqueuse

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330312A (ja) * 1994-06-03 1995-12-19 Idemitsu Petrochem Co Ltd 硫化リチウムの製造方法
US20060269844A1 (en) * 2005-05-26 2006-11-30 Ferro Corporation Triazine compounds for removing acids and water from nonaqueous electrolytes for electrochemical cells
US20100323240A1 (en) * 2007-03-12 2010-12-23 Central Glass Company, Limited Method for Producing Lithium Difluorophosphate and Nonaqueous Electrolyte Battery Using the Same
US20160149262A1 (en) * 2014-11-20 2016-05-26 Coorstek Fluorochemicals, Inc. Concentrated electrolyte solution

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8076033B2 (en) * 2004-10-19 2011-12-13 Mitsubishi Chemical Corporation Method for producing difluorophosphate, nonaqueous electrolyte solution for secondary battery and nonaqueous electrolyte secondary battery
WO2012118063A1 (fr) * 2011-03-03 2012-09-07 日本曹達株式会社 Procédé de fabrication de sel de sulfonylimide contenant du fluor
CN102786443B (zh) * 2011-05-20 2015-04-15 华中科技大学 二元或三元含氟磺酰亚胺的碱金属盐和离子液体及其应用
KR101640634B1 (ko) * 2013-01-31 2016-07-18 주식회사 엘지화학 비수 전해액 및 이를 포함하는 리튬 이차 전지

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07330312A (ja) * 1994-06-03 1995-12-19 Idemitsu Petrochem Co Ltd 硫化リチウムの製造方法
US20060269844A1 (en) * 2005-05-26 2006-11-30 Ferro Corporation Triazine compounds for removing acids and water from nonaqueous electrolytes for electrochemical cells
US20100323240A1 (en) * 2007-03-12 2010-12-23 Central Glass Company, Limited Method for Producing Lithium Difluorophosphate and Nonaqueous Electrolyte Battery Using the Same
US20160149262A1 (en) * 2014-11-20 2016-05-26 Coorstek Fluorochemicals, Inc. Concentrated electrolyte solution

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3577710A4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109742455A (zh) * 2018-12-24 2019-05-10 深圳市量能科技有限公司 一种锂离子电池的制作方法
CN109734061A (zh) * 2019-02-14 2019-05-10 湖南福邦新材料有限公司 一种双氟磺酰亚胺锂的制备方法
CN115335543A (zh) * 2020-03-06 2022-11-11 内华达高等教育系统董事会代表拉斯维加斯内华达大学 从溶解在离子液体中的锂盐回收锂
WO2023276812A1 (fr) 2021-06-30 2023-01-05 株式会社日本触媒 Procédé de production de composition et solution électrolytique non aqueuse
KR20240025009A (ko) 2021-06-30 2024-02-26 가부시키가이샤 닛폰 쇼쿠바이 조성물의 제조방법 및 비수전해액

Also Published As

Publication number Publication date
EP3577710A4 (fr) 2020-12-23
CN110870125A (zh) 2020-03-06
KR20190110608A (ko) 2019-09-30
EP3577710A1 (fr) 2019-12-11

Similar Documents

Publication Publication Date Title
US10505228B2 (en) Method for drying electrolyte solution
CN106976849B (zh) 一种双氟磺酰亚胺锂的提纯方法
WO2018144480A1 (fr) Procédé de production d'une solution électrolytique de sel métallique alcalin hygroscopique
KR102337612B1 (ko) Lifsi 의 건조 및 정제 방법
KR101361701B1 (ko) 플루오로설포닐이미드의 알칼리 금속염 및 그 제조방법
CN109941982B (zh) 一种二氟磷酸锂的提纯方法
JP6370852B2 (ja) ジスルホニルアミド塩の顆粒または粉末
JP2004511068A (ja) 有機液体電解質を乾燥する方法
UA123732C2 (uk) Спосіб одержання 2-[4-(4-хлорфенокси)-2-(трифторметил)феніл]-1-(1,2,4-триазол-1-іл)пропан-2-олу
JPH10338653A (ja) 液体の脱水方法
CN111057079A (zh) 一种双草酸硼酸锂的提纯方法及双草酸硼酸锂
KR20200049164A (ko) 매우 효율적인 리튬 비스(플루오로술포닐)이미드의 새로운 제조방법
CN105801554A (zh) 高纯度氟代碳酸乙烯酯的提纯方法
CN112166104A (zh) 制备含有氟磺酰基基团的酰亚胺盐的方法
CN106829908B (zh) 一种二氟磷酸锂的制备方法及含有二氟磷酸锂的锂离子电池非水电解液
KR20140102248A (ko) Lipf6 용액
JP3555720B2 (ja) ヘキサフルオロリン酸リチウムの付加化合物及びその製造方法並びにそれを用いた電解液
JPH11157830A (ja) テトラフルオロホウ酸リチウムの製造方法
CN114380305A (zh) 一种在双氟磺酰亚胺锂的生产中回收原辅材料的方法
WO2018174196A1 (fr) Procédé de stabilisation d'une composition contenant du carbonate d'éthylène de haute pureté
US20240017999A1 (en) Method for recovering raw and auxiliary materials in the production of lithium bis(fluorosulfonyl)imide
WO2022014501A1 (fr) Solution non aqueuse d'iodure de lithium, iodure de lithium, solvate non aqueux d'iodure de lithium, procédé de production d'une solution non aqueuse d'iodure de lithium, procédé de production d'iodure de lithium et procédé de production d'un solvate non aqueux d'iodure de lithium
WO2023142025A1 (fr) Bis(fluorosulfonyl)imide de lithium, son procédé de préparation, électrolyte et batterie secondaire
JP6441662B2 (ja) ヨウ化アルカリ金属またはヨウ化アルカリ土類金属の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18748078

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20197025560

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018748078

Country of ref document: EP

Effective date: 20190902