CN102532176A - Ammonium oxalyldifluoro borate electrolyte and preparation method and purification method thereof - Google Patents
Ammonium oxalyldifluoro borate electrolyte and preparation method and purification method thereof Download PDFInfo
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Abstract
Embodiments of the invention disclose an ammonium oxalyldifluoro borate electrolyte and a preparation method and a purification method thereof; the preparation method comprises the following steps: mixing quaternary ammonium base with oxalic acid, reacting to obtain an ammonium oxalate salt; mixing the ammonium oxalate salt with boron trifluoride ether in a first organic solvent, reacting at 10-120 DEG C to obtain the ammonium oxalyldifluoro borate electrolyte. The preparation method has a mild reaction condition, simple operation, high product purity, and low cost, and facilitates industrialization. The ammonium oxalyldifluoro borate electrolyte prepared in the invention has excellent properties of both quaternary ammonium compounds and oxalyldifluoro borate compounds; ammonium oxalyldifluoro borate is easy to dissolve in water and organic solvents, has high conductivity in organic solutions, can be used as an electrolyte of energy storage devices such as lithium batteries and super capacitors which have high requirements for electrolyte salt purity, and can improve the electrochemical performance of energy storage devices.
Description
Technical field
The present invention relates to the ionogen technical field, more particularly, relate to a kind of difluoro oxalate ammonium borate class ionogen and preparation method thereof and purification process.
Background technology
In recent years, because the pressure of environmental pollution and energy shortage, various countries strive to find the energy of environmental protection, Sustainable development.Energy storage devices such as the lithium ion battery of the green high-capacity environment-protecting that occurs the nineties in 20th century and ultracapacitor, owing to have the energy density height, have extended cycle life, the WP advantages of higher, become one of power source that attracts most attention.
Ionogen is the important component part in the energy storage device, in energy storage device, is bearing between the positive and negative electrode effect of transmission ionic, and the characteristics such as capacity, operating temperature range, cycle performance and safety performance of energy storage device are had significant effects.With the difluoro oxalate borate is the ionogen of negative ion; See from molecular configuration, be two oxalic acid borates and two kinds of ionic of tetrafluoroborate separately half textural association thereby have the characteristic of two oxalic acid ammonium borates and two kinds of compounds of ammonium borofluoride together; Solubleness is high, and viscosity is low.Therefore, be that the ionogen of negative ion can be applied in the electrolytic solution like energy storage devices such as lithium cell and ultracapacitors with the difluoro oxalate borate, make energy storage device have higher specific conductivity, very wide and stable potential window and good charging and discharging performance.
At present, public reported is that the ionogen of negative ion is mainly difluorine oxalic acid boracic acid lithium etc. with the difluoro oxalate borate.For example, application number a kind of preparation method of difluorine oxalic acid boracic acid lithium that has been 200710132873.8 Chinese patent bibliographical information.This method is reacted fluorochemicals, boron-containing compound, lithium-containing compound and the compound that contains oxalate under certain temperature and pressure; Generate the difluorine oxalic acid boracic acid lithium bullion; Carry out purification by liquid extraction with organic solvent then, obtain the cell-grade difluorine oxalic acid boracic acid lithium carrying out recrystallization and vacuum-drying at last.
The synthesis technique of application number a kind of difluorine oxalic acid boracic acid lithium that has been 200910144762.8 Chinese patent bibliographical information and LiBF4; This technology with the compound of fluorine-containing compound, boracic, the compound that contains the compound of lithium and contain oxalate 0～100 ℃, reaction pressure be 0.1～1MPa, and reaction medium in react; Wherein the mol ratio of elemental lithium, fluorine element, boron and oxalate denominationby is 2～3: 5～6: 2: 1; Generation contains the reaction solution of difluorine oxalic acid boracic acid lithium and LiBF4; Difluorine oxalic acid boracic acid lithium in the reaction solution and LiBF4 are carried out initial gross separation; Carry out extracting and separating with the organic solvent that can extract difluorine oxalic acid boracic acid lithium or LiBF4 then, carry out recrystallization and vacuum-drying respectively and obtain difluorine oxalic acid boracic acid lithium and LiBF4.
The synthesis technique of application number a kind of difluorine oxalic acid boracic acid lithium that has been 200910144760.9 Chinese patent bibliographical information and di-oxalate lithium borate.This synthesis technique comprises the steps: that be to react in 0.1～1Mpa and the reaction medium the compound of fluorine-containing compound, boracic, the compound that contains the compound of lithium and contain oxalate at 0～100 ℃, reaction pressure, and wherein the mol ratio of elemental lithium, fluorine element, boron and oxalate denominationby is 5～9: 5～9: 2～3: 3～4; Generation contains the reaction solution of difluorine oxalic acid boracic acid lithium and di-oxalate lithium borate; Difluorine oxalic acid boracic acid lithium in the reaction solution and di-oxalate lithium borate are carried out initial gross separation, carry out further extracting and separating with the organic solvent that can extract difluorine oxalic acid boracic acid lithium or di-oxalate lithium borate then; Carry out recrystallization and vacuum-drying respectively and obtain the difluorine oxalic acid boracic acid lithium and the di-oxalate lithium borate of cell-grade.
But what report in the prior art is in the ionogen of negative ion with the difluoro oxalate borate, not about the report of difluoro oxalate ammonium borate class ionogen and preparation method thereof with the purification process aspect.
Summary of the invention
In view of this; The technical problem that the present invention will solve is to provide a kind of difluoro oxalate ammonium borate class ionogen and preparation method thereof and purification process; This preparation method is simple to operate, and the difluoro oxalate ammonium borate class ionogen purity that the present invention obtains is high, can be used in the electrolytic solution of energy storage device.
The present invention provides a kind of difluoro oxalate ammonium borate electrolytelike preparation method, comprising:
Step a) is mixed quaternary ammonium hydroxide with oxalic acid, reaction obtains the oxalic acid ammonium salt;
Step b) is that 0.9～1.1: 0.9～1.1 said oxalic acid ammonium salt mixes in first organic solvent with BFEE with mol ratio, under 10～120 ℃ of conditions, reacts, and obtains difluoro oxalate ammonium borate class ionogen.
Preferably, also comprise:
The difluoro oxalate ammonium borate class ionogen heating that step c) obtains step b), first organic solvent is removed in evaporation;
The product that step d) obtains step c) is used second organic solvent dissolution; Stir; Filter, remove second organic solvent, said second organic solvent is any one or two kinds in alcohol compound, nitrile compounds, compound fragrant hydrocarbon, ester compound and the ketone compounds.
Preferably, said second organic solvent is that volume ratio is that 1: 1～5 alcohol compound and nitrile compounds, volume ratio are that 2～3: 1 alcohol compound and compound fragrant hydrocarbon, volume ratio are that 1～3: 1 alcohol compound and ketone compounds, volume ratio are that 1～3: 1 nitrile compounds and ketone compounds, volume ratio are that 3～6: 1 nitrile compounds and compound fragrant hydrocarbon, volume ratio are that 1～4: 1 ester compound and compound fragrant hydrocarbon, volume ratio are that 2～6: 1 ester compound and nitrile compounds, volume ratio are that 1: 1～3 ester compound and ketone compounds, volume ratio are that 2～6: 1 ketone compounds and compound fragrant hydrocarbon or volume ratio are 1: 1～3 alcohol compound and ester compound.
Preferably, said step a) is specially:
Be that 0.9～1.1: 1.9～2.1 quaternary ammonium hydroxide mixes with oxalic acid with mol ratio, stir, be heated to, reacted 1～3 hour, be heated to 70～80 ℃ then, obtain the oxalic acid ammonium salt at 50～65 ℃.
Preferably, said quaternary ammonium hydroxide is TMAH, tetraethyl ammonium hydroxide or TBAH.
Preferably, the reaction times is 2～120 hours in the said step b).
The present invention also provides a kind of difluoro oxalate ammonium borate electrolytelike method of purification, comprising:
Difluoro oxalate ammonium borate class ionogen to be purified is carried out crystallization with solvent, and suction filtration, said solvent are any three kinds in alcohol compound, nitrile compounds, compound fragrant hydrocarbon, ester compound and the ketone compounds;
Product recrystallization, drying that suction filtration is obtained.
Preferably, said solvent is that volume ratio is 2: 1: 2 acetonitrile, toluene and an acetone; Volume ratio is 2: 1: 2 acetonitrile, diethyl carbonate and an acetone; Volume ratio is 3: 1: 1 acetonitrile, toluene and an acetone; Volume ratio is 3: 1: 1 acetonitrile, acetone and a methylcarbonate; Volume ratio is 4: 1: 1 acetonitrile, toluene and a diethyl carbonate; Volume ratio is 3: 1: 1 acetonitrile, 2-butanone and a methylcarbonate; Volume ratio is 1: 1: 1 acetonitrile, 2-butanone and a methyl alcohol; Volume ratio is acetonitrile, Virahol and the acetone that 1: 1: 2 acetonitrile, Virahol and methyl alcohol or volume ratio is 2: 1: 2.
Preferably, said crystalline temperature is-50～5 ℃.
The present invention also provides a kind of difluoro oxalate ammonium borate class ionogen, has suc as formula the structure shown in the I:
The formula I,
Wherein, R
1, R
2, R
3And R
4Be alkyl independently separately.
Can find out that from above-mentioned technical scheme the present invention provides a kind of difluoro oxalate ammonium borate class ionogen and preparation method thereof, this method is mixed quaternary ammonium hydroxide with oxalic acid, and reaction obtains the oxalic acid ammonium salt; Then the oxalic acid ammonium salt is mixed in first organic solvent with BFEE, under 10～120 ℃ of conditions, react, obtain difluoro oxalate ammonium borate class ionogen.This preparing method's reaction conditions is gentle, and is simple to operate, and product purity is high, cost is low, helps industriallization.The difluoro oxalate ammonium borate class ionogen of the present invention's preparation has the good characteristic of quarternary ammonium salt compound and difluoro oxalate boric acid ester compound concurrently; Soluble in water and the organic solvent of difluoro oxalate ammonium borate; And in organic solution, possesses higher conductive capability; Can be used for improving the chemical property of energy storage device in the electrolytic solution to energy storage devices such as high lithium cell of electrolytic salt purity requirement and ultracapacitors.
The present invention also provides a kind of difluoro oxalate ammonium borate electrolytelike method of purification; Comprise: difluoro oxalate ammonium borate class ionogen that will be to be purified carries out crystallization, suction filtration with solvent, and said solvent is any three kinds in alcohol compound, nitrile compounds, compound fragrant hydrocarbon, ester compound and the ketone compounds; Product recrystallization, drying that suction filtration is obtained.The present invention purifies through adopting mixed solvent, and the difluoro oxalate ammonium borate class ionogen purity that obtains is high, is suitable in the energy storage device electrolytic solution.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is the electrochemical window graphic representation of embodiment 1 disclosed tetramethyl-difluoro oxalate ammonium borate;
Fig. 2 is the electrochemical window graphic representation of embodiment 4 disclosed tetraethyl-difluoro oxalate ammonium borates;
Fig. 3 is the electrochemical window graphic representation of embodiment 7 disclosed tetrabutyl difluoro oxalate ammonium borates.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The present invention provides a kind of difluoro oxalate ammonium borate electrolytelike preparation method, comprising:
Step a) is mixed quaternary ammonium hydroxide with oxalic acid, reaction obtains the oxalic acid ammonium salt;
Step b) is that 0.9～1.1: 0.9～1.1 said oxalic acid ammonium salt mixes in first organic solvent with BFEE with mol ratio, under 10～120 ℃ of conditions, reacts, and obtains difluoro oxalate ammonium borate class ionogen.
Said step a) is preferably:
Be that 0.9～1.1: 1.9～2.1 quaternary ammonium hydroxide mixes with oxalic acid with mol ratio, stir, be heated to, reacted 1～3 hour, be heated to 70～80 ℃ then, obtain the oxalic acid ammonium salt at 50～65 ℃.The mol ratio of said quaternary ammonium hydroxide and oxalic acid more preferably 0.95～1.05: 1.95～2.05 most preferably is 1: 2.Said being heated at 50～65 ℃ more preferably is heated to 55～60 ℃, most preferably is 60 ℃.In more preferably 1～2 hour said reaction times, most preferably be 1 hour.Saidly be heated to 70～80 ℃ then and more preferably be heated to 70～75 ℃, most preferably be and be heated to 70 ℃.Said quaternary ammonium hydroxide is preferably TMAH, tetraethyl ammonium hydroxide, TBAH.Said first organic solvent is preferably methyl alcohol, ethanol or ether.
With R
1, R
2, R
3And R
4Independently for methyl is an example, difluoro oxalate ammonium borate class preparation of electrolyte process is as follows separately:
Because the tetramethyl-ammonium oxalate is soluble in alcohols, and oxalic acid is slightly soluble in alcohols at normal temperatures, therefore, R
1, R
2, R
3And R
4When independently being methyl separately, preferably with alcohols purification tetramethyl-ammonium oxalate.
After obtaining the tetramethyl-ammonium oxalate, with tetramethyl-ammonium oxalate and BFEE reaction, reaction formula is following:
Utilize the difference of the solubleness of above-mentioned resultant in different solvents, product is separated.
According to the present invention, the mol ratio of oxalic acid ammonium salt and BFEE is preferably 0.95～1.05 described in the said step b): 0.95～1.05, and more preferably 1: 1.Temperature of reaction is preferably 30～100 ℃ in the said step b), more preferably 40～90 ℃, most preferably is 50～80 ℃.The said reaction times is preferably 2～120 hours, more preferably 20～90 hours, most preferably is 30～80 hours.
According to the present invention, preferably also comprise:
The difluoro oxalate ammonium borate class ionogen heating that step c) obtains step b), first organic solvent is removed in evaporation;
The product that step d) obtains step c) is used second organic solvent dissolution; Stir; Filter, remove second organic solvent, said second organic solvent is any one or two kinds in alcohol compound, nitrile compounds, compound fragrant hydrocarbon, ester compound and the ketone compounds.
It is 1: 1～5 alcohol compound and nitrile compounds that said second organic solvent is preferably volume ratio; Volume ratio is 2～3: 1 alcohol compound and compound fragrant hydrocarbon; Volume ratio is 1～3: 1 alcohol compound and ketone compounds; Volume ratio is 1～3: 1 nitrile compounds and ketone compounds; Volume ratio is 3～6: 1 nitrile compounds and compound fragrant hydrocarbon; Volume ratio is 1～4: 1 ester compound and compound fragrant hydrocarbon; Volume ratio is 2～6: 1 ester compound and nitrile compounds; Volume ratio is 1: 1～3 ester compound and ketone compounds; Volume ratio is that 2～6: 1 ketone compounds and compound fragrant hydrocarbon or volume ratio are 1: 1～3 alcohol compound and ester compound.
The invention discloses a kind of difluoro oxalate ammonium borate class ionogen, have the structure shown in the formula I:
The formula I,
Wherein, R
1, R
2, R
3And R
4Be alkyl independently separately.
Said R
1Be preferably methyl, ethyl, propyl group or butyl; Said R
2Be preferably methyl, ethyl, propyl group or butyl; Said R
3Be preferably methyl, ethyl, propyl group or butyl; Said R
4Be preferably methyl, ethyl, propyl group or butyl.
The present invention provides a kind of difluoro oxalate ammonium borate class ionogen and preparation method thereof, and this method is mixed quaternary ammonium hydroxide with oxalic acid, and reaction obtains the oxalic acid ammonium salt; Then the oxalic acid ammonium salt is mixed in first organic solvent with BFEE; Under 10～120 ℃ of conditions, react, the reaction conditions that obtains this preparation method of difluoro oxalate ammonium borate class ionogen is gentle, simple to operate; Product purity is high, cost is low, helps industriallization.The difluoro oxalate ammonium borate class ionogen of the present invention's preparation has the good characteristic of quarternary ammonium salt compound and difluoro oxalate boric acid ester compound concurrently; Soluble in water and the organic solvent of difluoro oxalate ammonium borate; And in organic solution, possesses higher conductive capability; Can be used for improving the chemical property of energy storage device in the electrolytic solution to energy storage devices such as high lithium cell of electrolytic salt purity requirement and ultracapacitors.
The present invention also provides a kind of difluoro oxalate ammonium borate electrolytelike method of purification, comprising:
Difluoro oxalate ammonium borate class ionogen to be purified is carried out crystallization, suction filtration with solvent, and said solvent is any three kinds in alcohol compound, nitrile compounds, compound fragrant hydrocarbon, ester compound and the ketone compounds;
With product recrystallization, the drying that suction filtration obtains, obtain difluoro oxalate ammonium borate compound.
Said crystallization is preferably low temperature crystallization, and temperature is preferably-50～5 ℃, more preferably-40～0 ℃, most preferably is-30～-10 ℃.
The present invention selects suitable solvent, has reached the effect of good purification.Said solvent is preferably any three kinds in acetonitrile, toluene, acetone, diethyl carbonate, methylcarbonate, 2-butanone, methyl alcohol and the Virahol, and more preferably volume ratio is 2: 1: 2 acetonitrile, toluene and an acetone; Volume ratio is 2: 1: 2 acetonitrile, diethyl carbonate and an acetone; Volume ratio is 3: 1: 1 acetonitrile, toluene and an acetone; Volume ratio is 3: 1: 1 acetonitrile, acetone and a methylcarbonate; Volume ratio is 4: 1: 1 acetonitrile, toluene and a diethyl carbonate; Volume ratio is 3: 1: 1 acetonitrile, 2-butanone and a methylcarbonate; Volume ratio is 1: 1: 1 acetonitrile, 2-butanone and a methyl alcohol; Volume ratio is acetonitrile, Virahol and the acetone that 1: 1: 2 acetonitrile, Virahol and methyl alcohol or volume ratio is 2: 1: 2.
Said product recrystallization, the drying that suction filtration is obtained preferably is specially:
The product that suction filtration is obtained is low temperature recrystallization 2～10 times and 60～70 ℃ of vacuum-dryings 30～80 hours repeatedly, more preferably the product that obtains of suction filtration low temperature recrystallization 3～8 times and 65 ℃ of vacuum-dryings 40～60 hours repeatedly just.
The invention provides a kind of method of purification,, obtained highly purified difluoro oxalate ammonium borate class ionogen, be suitable in the energy storage device electrolytic solution through purifying with mixed solvent.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Embodiment 1
Step a) adds 0.1mol tetramethylammonium hydroxide aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 60 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetramethyl-ammonium oxalate solid;
Step b) is dissolved tetramethyl-ammonium oxalate solid with methyl alcohol at normal temperatures; Filter, remove insolubles, then tetramethyl-ammonium oxalate methanol solution is settled to 200ml; Pack in the 500ml round-bottomed flask; BFEE with 0.1mol under the stirring at normal temperature condition is added drop-wise in the tetramethyl-ammonium oxalate methanol solution, drips to finish the back 70 ℃ of following heated and stirred, reacts 12 hours;
Step c) is removed methyl alcohol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
It is 1: 1 methyl alcohol and the mixed solvent dissolving step c of acetonitrile that step d) is used volume ratio) solid that obtains, stirring at normal temperature removes by filter insoluble impurity, and the gained filtrate decompression is distilled, and obtains tetramethyl-difluoro oxalate boric acid ammonium salt.
Using volume ratio is that 2: 1: 2 the mixed solvent of acetonitrile, toluene, acetone is to the above-mentioned tetramethyl-difluoro oxalate boric acid ammonium salt dissolving that obtains, at 0 ℃ of crystallization, suction filtration; Obtain tetramethyl-difluoro oxalate boric acid ammonium salt crystal; Recrystallization 5 times 65 ℃ of vacuum-dryings 48 hours, obtains highly purified tetramethyl-difluoro oxalate ammonium borate (TMAODFB) salt crystal; Structural formula is suc as formula shown in the II
The formula II.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in the tetramethyl-difluoro oxalate ammonium borate of analyses the present invention preparation.Experimental result is shown in table 1 and table 2, and therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product tetramethyl-difluoro oxalate ammonium borate.
Characterize the tetramethyl-difluoro oxalate ammonium borate purity of the present invention's preparation indirectly through electro-chemical test.With 1,2-Ucar 35 carbonic ether is made into electrolytic solution, on electrochemical workstation, carries out the electrochemical potential window and tests with the difluoro oxalate ammonium borate of present embodiment preparation; Test result is as shown in Figure 1, and as can beappreciated from fig. 1, the electrochemical window scope of TMAODFB is-4.3～3V; In the electrochemical window scope, line smoothing does not have obvious redox peak and occurs; The tetramethyl-difluoro oxalate ammonium borate purity that the present embodiment preparation is described is high, is suitable in the energy storage device electrolytic solution.
Step a) adds 0.1mol tetramethylammonium hydroxide aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 60 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetramethyl-ammonium oxalate solid;
Step b) is dissolved tetramethyl-ammonium oxalate solid with methyl alcohol at normal temperatures; Filter, remove insolubles, again tetramethyl-ammonium oxalate methanol solution is settled to 200ml; Pack in the 500ml round-bottomed flask; BFEE with 0.1mol under the stirring at normal temperature condition is added dropwise in the tetramethyl-ammonium oxalate methanol solution, drips to finish the back 60 ℃ of following heated and stirred, reacts 12 hours;
Step c) is removed methyl alcohol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
Step d) use ratio is 1: 1 ethanol and diethyl carbonate mixed solvent dissolving step c) solid that obtains, stirring at normal temperature removes by filter insoluble impurity, with the distillation of gained filtrate decompression, obtains tetramethyl-difluoro oxalate boric acid ammonium salt.
Using volume ratio is 2: 1: 2 acetonitrile, diethyl carbonate, the above-mentioned tetramethyl-difluoro oxalate boric acid ammonium salt that obtains of mixed solvent dissolving of acetone;-5 ℃ of crystallizations; Suction filtration obtains tetramethyl-difluoro oxalate boric acid ammonium salt crystal, low temperature recrystallization 6 times; 65 ℃ of vacuum-dryings 48 hours, obtain tetramethyl-difluoro oxalate ammonium borate (TMAODFB) salt crystal.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in the tetramethyl-difluoro oxalate ammonium borate of analyses the present invention preparation.Experimental result shows, therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product difluoro oxalate ammonium borate.
Embodiment 3
Step a) adds 0.1mol tetramethylammonium hydroxide aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 60 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetramethyl-ammonium oxalate solid;
Step b) is dissolved tetramethyl-ammonium oxalate solid with methyl alcohol at normal temperatures; Filter, remove insolubles, then tetramethyl-ammonium oxalate methanol solution is settled to 200ml; Pack in the 500ml round-bottomed flask; BFEE with 0.1mol under the stirring at normal temperature condition is added drop-wise in the tetramethyl-ammonium oxalate methanol solution, drips to finish the back 60 ℃ of following heated and stirred, reacts 12 hours;
Step c) is removed methyl alcohol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
It is the mixed solvent dissolving step c of 2: 1: 1 methyl alcohol, Virahol and 2-butanone that step d) is used volume ratio) solid that obtains, stirring at normal temperature removes by filter insoluble impurity, with the distillation of gained filtrate decompression, obtains tetramethyl-difluoro oxalate boric acid ammonium salt.
Using volume ratio is 3: 1: 1 acetonitrile, toluene, the above-mentioned tetramethyl-difluoro oxalate boric acid ammonium salt that obtains of mixed solvent dissolving of acetone;-15 ℃ of crystallizations; Suction filtration; Obtain tetramethyl-difluoro oxalate boric acid ammonium salt crystal, recrystallization 4 times also obtained high purity tetramethyl-difluoro oxalate ammonium borate (TMAODFB) salt crystal in 48 hours 65 ℃ of vacuum-dryings.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in the tetramethyl-difluoro oxalate ammonium borate of analyses the present invention preparation.Experimental result shows, therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product difluoro oxalate ammonium borate.
Step a) adds the 0.1mol tetraethyl ammonium hydroxide aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 50 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetraethyl-ammonium oxalate solid;
Step b) is dissolved tetraethyl-ammonium oxalate solid with ether at normal temperatures; Filter, remove insolubles, again tetraethyl-ammonium oxalate diethyl ether solution is settled to 200ml; Pack in the 500ml round-bottomed flask; Under the stirring at normal temperature condition, the BFEE of 0.1mol is added dropwise in the tetraethyl-ammonium oxalate diethyl ether solution, drip and finish the back 60 ℃ of following heated and stirred reactions 12 hours;
Step c) is removed ether with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
It is 1: 1 ethanol and isopropyl alcohol mixed solvent dissolving step c that step d) is used volume ratio) solid that obtains, stirring at normal temperature removes by filter insoluble impurity, and the gained filtrate decompression is distilled, and obtains tetraethyl-difluoro oxalate boric acid ammonium salt.
The use volume ratio is that the mixed solvent of 3: 1: 1 acetonitrile, acetone and methylcarbonate dissolves the above-mentioned tetraethyl-difluoro oxalate boric acid ammonium salt that obtains;-20 ℃ of crystallizations, suction filtration obtains tetraethyl-difluoro oxalate boric acid ammonium salt crystal; Recrystallization 6 times; And obtaining high purity tetraethyl-difluoro oxalate ammonium borate (TEAODFB) salt crystal in 48 hours 65 ℃ of vacuum-dryings, structural formula is suc as formula shown in the III
The formula III.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in the tetraethyl-difluoro oxalate ammonium borate (TEAODFB) of analyses the present invention preparation.Experimental result is shown in table 1 and table 2, and therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product tetraethyl-difluoro oxalate ammonium borate.
Characterize the tetraethyl-difluoro oxalate ammonium borate purity of the present invention's preparation indirectly through electro-chemical test.With 1,2-Ucar 35 carbonic ether is made into electrolytic solution, on electrochemical workstation, carries out the electrochemical potential window and tests with the difluoro oxalate ammonium borate of present embodiment preparation; Test result is as shown in Figure 2, and as can beappreciated from fig. 2, the electrochemical window scope of TEAODFB is-3.9～3.4V; In the electrochemical window scope, line smoothing does not have obvious redox peak and occurs; The tetraethyl-difluoro oxalate ammonium borate purity that the present embodiment preparation is described is high, is suitable in the energy storage device electrolytic solution.
Embodiment 5
Step a) adds the 0.1mol tetraethyl ammonium hydroxide aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 50 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetraethyl-ammonium oxalate solid;
Step b) is dissolved tetraethyl-ammonium oxalate solid with ethanol at normal temperatures; Filter, remove insolubles, again tetraethyl-ammonium oxalate ethanolic soln is settled to 200ml; Pack in the 500ml round-bottomed flask; Under the stirring at normal temperature condition, the BFEE of 0.1mol is added dropwise in the reactant, drip and finish the back 60 ℃ of following heated and stirred reactions 12 hours;
Step c) is removed ethanol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
It is 1: 1 ethanol and acetone mixed solvent dissolving step c that step d) is used volume ratio) solid that obtains, stirring at normal temperature removes by filter insoluble impurity, and the gained filtrate decompression is distilled, and obtains tetraethyl-difluoro oxalate boric acid ammonium salt.
The use volume ratio is that 4: 1: 1 acetonitrile, toluene and diethyl carbonate mixed solvent dissolves the above-mentioned tetraethyl-difluoro oxalate boric acid ammonium salt that obtains;-30 ℃ of crystallizations; Suction filtration; Obtain tetraethyl-difluoro oxalate boric acid ammonium salt crystal, recrystallization 5 times, and obtained high purity tetraethyl-difluoro oxalate ammonium borate (TEAODFB) salt crystal in 48 hours 65 ℃ of vacuum-dryings.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in the tetraethyl-difluoro oxalate ammonium borate (TEAODFB) of analyses the present invention preparation.Experimental result shows, therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product tetraethyl-difluoro oxalate ammonium borate.
Step a) adds the 0.1mol tetraethyl ammonium hydroxide aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 50 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetraethyl-ammonium oxalate solid;
Step b) is dissolved with methyl alcohol at normal temperatures, and tetraethyl-ammonium oxalate solid is dissolved at normal temperatures, filters; Remove insolubles; Again tetraethyl-ammonium oxalate methanol solution is settled to 200ml, in the 500ml round-bottomed flask of packing into, under the stirring at normal temperature condition; The BFEE of 0.1mol is added dropwise in the reactant, drips and finish the back 60 ℃ of following heated and stirred reactions 12 hours;
Step c) is removed methyl alcohol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
It is 2: 1 acetonitrile and acetone mixed solvent dissolving step c that step d) is used volume ratio) solid that obtains, stirring at normal temperature removes by filter insoluble impurity, and the gained filtrate decompression is distilled, and obtains tetraethyl-difluoro oxalate boric acid ammonium salt.
Use volume ratio be 3: 1: 1 acetonitrile, 2-butanone and methylcarbonate the mixed solvent dissolving and carry out low temperature crystallization;-10 ℃ of crystallizations; Suction filtration; Obtain tetraethyl-difluoro oxalate boric acid ammonium salt crystal, recrystallization 4 times, and obtained high purity tetraethyl-difluoro oxalate ammonium borate (TEAODFB) salt crystal in 48 hours 65 ℃ of vacuum-dryings.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in the tetraethyl-difluoro oxalate ammonium borate (TEAODFB) of analyses the present invention preparation.Experimental result shows, therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product tetraethyl-difluoro oxalate ammonium borate.
Embodiment 7
Step a) adds the 0.1mol TBAH aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 50 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetrabutyl ammonium oxalate solid;
Step b) is dissolved tetrabutyl ammonium oxalate solid with methyl alcohol at normal temperatures; Filter, remove insolubles, again tetrabutyl ammonium oxalate methanol solution is settled to 200ml; Pack in the 500ml round-bottomed flask; Under the stirring at normal temperature condition, the BFEE of 0.1mol is added dropwise in the reactant, drip and finish the back 70 ℃ of following heated and stirred reactions 12 hours;
Step c) is removed methyl alcohol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
It is the mixed solvent dissolving step c of 1: 1 ethanol and acetone that step d) is used volume ratio) solid that obtains, stirring at normal temperature removes by filter insoluble impurity, and the gained filtrate decompression is distilled, and obtains tetrabutyl difluoro oxalate boric acid ammonium salt.
Using volume ratio is that 1: 1: 1 the mixed solvent of acetonitrile, 2-butanone and methyl alcohol is to the above-mentioned tetrabutyl difluoro oxalate boric acid ammonium salt dissolving that obtains and-15 ℃ of crystallizations; Suction filtration; Obtain tetrabutyl difluoro oxalate boric acid ammonium salt crystal, recrystallization 5 times, and obtained high purity tetrabutyl difluoro oxalate ammonium borate (TBAODFB) salt crystal in 48 hours 65 ℃ of vacuum-dryings; Structural formula is suc as formula shown in the IV
The formula IV.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in tetrabutyl difluoro oxalate ammonium borate (TBAODFB) salt of analyses the present invention preparation.Experimental result is shown in table 1 and table 2, and therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product tetrabutyl difluoro oxalate ammonium borate.
Characterize the tetrabutyl difluoro oxalate ammonium borate purity of the present invention's preparation indirectly through electro-chemical test.With the difluoro oxalate ammonium borate of present embodiment preparation with 1; 2-Ucar 35 carbonic ether is made into electrolytic solution, on electrochemical workstation, carries out the test of electrochemical potential window, and test result is as shown in Figure 3; As can beappreciated from fig. 3, the electrochemical window scope of TBAODFB is-4.2～2.5V.In the electrochemical window scope, line smoothing does not have obvious redox peak and occurs, and explains that material purity is high, is suitable in the energy storage device electrolytic solution.
Step a) adds the 0.1mol TBAH aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 50 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetrabutyl ammonium oxalate solid;
Step b) is dissolved tetrabutyl ammonium oxalate solid with methyl alcohol at normal temperatures; Filter, remove insolubles, again tetrabutyl ammonium oxalate methanol solution is settled to 200ml; Pack in the 500ml round-bottomed flask; Under the stirring at normal temperature condition, the BFEE of 0.1mol is added dropwise in the tetrabutyl ammonium oxalate methanol solution, drip and finish the back 70 ℃ of following heated and stirred reactions 12 hours;
Step c) is removed methyl alcohol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
It is the solid that the mixed solvent step c) of 3: 1 acetonitrile and toluene obtains that step d) is used volume ratio, and stirring at normal temperature removes by filter insoluble impurity, and the gained filtrate decompression is distilled, and obtains tetrabutyl difluoro oxalate boric acid ammonium salt.
Using volume ratio is that 1: 1: 2 the mixed solvent of acetonitrile, Virahol and methyl alcohol is to the above-mentioned tetrabutyl difluoro oxalate boric acid ammonium salt dissolving that obtains and carry out-10 ℃ of crystallizations; Suction filtration; Obtain tetrabutyl difluoro oxalate boric acid ammonium salt crystal; Recrystallization 5 times, and obtained high purity tetrabutyl difluoro oxalate ammonium borate (TBAODFB) salt crystal in 48 hours 65 ℃ of vacuum-dryings.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in tetrabutyl difluoro oxalate ammonium borate (TBAODFB) salt of analyses the present invention preparation.Experimental result shows, therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product tetrabutyl difluoro oxalate ammonium borate.
Embodiment 9
Step a) adds the 0.1mol TBAH aqueous solution and 0.05mol oxalic acid in the round-bottomed flask, is heated to 50 ℃, stirs, and reacts 1 hour, is heated to 70 ℃ then, and moisture is removed in evaporation, obtains tetrabutyl ammonium oxalate solid;
Step b) is dissolved tetrabutyl ammonium oxalate solid with methyl alcohol at normal temperatures; Filter, remove insolubles, again tetrabutyl ammonium oxalate methanol solution is settled to 200ml; Pack in the 500ml round-bottomed flask; Under the stirring at normal temperature condition, the BFEE of 0.1mol is added dropwise in the reactant, drip and finish the back 70 ℃ of following heated and stirred reactions 12 hours;
Step c) is removed methyl alcohol with the product heating evaporation that step b) obtains, and stops heating to separating out solid;
Step d) use volume ratio is 3: 1 acetone and toluene mixed solvent dissolving step c) obtain, stirring at normal temperature removes by filter insoluble impurity, with the distillation of gained filtrate decompression, obtains tetrabutyl difluoro oxalate boric acid ammonium salt.
Using volume ratio is that 2: 1: 2 acetonitrile, Virahol and acetone mixed solvent is to the above-mentioned tetrabutyl difluoro oxalate boric acid ammonium salt dissolving that obtains and-20 ℃ of crystallizations; Suction filtration; Obtain tetrabutyl difluoro oxalate boric acid ammonium salt crystal; Recrystallization 5 times, and obtained high purity tetrabutyl difluoro oxalate ammonium borate (TBAODFB) salt crystal in 48 hours 65 ℃ of vacuum-dryings.
With carbon, hydrogen, the ratio of nitrogen element in entire compound in tetrabutyl difluoro oxalate ammonium borate (TBAODFB) salt of analyses the present invention preparation.Experimental result shows, therefore experimental value and theoretical value basically identical, prove that the synthetic molecules structure is a title product tetrabutyl difluoro oxalate ammonium borate.
The electrolytelike experimental value result of table 1 analyses difluoro oxalate ammonium borate
The electrolytelike theoretical value result of table 2 analyses difluoro oxalate ammonium borate
Can find out that from the foregoing description the preparation method that the present invention adopts is simple to operate, reaction conditions is gentle, only needs synthesis under normal pressure to carry out.The difluoro oxalate ammonium borate class ionogen purity of the present invention's preparation is high, can be used in the electrolytic solution of energy storage device.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the electrolytelike preparation method of difluoro oxalate ammonium borate is characterized in that, comprising:
Step a) is mixed quaternary ammonium hydroxide with oxalic acid, reaction obtains the oxalic acid ammonium salt;
Step b) is that 0.9～1.1: 0.9～1.1 said oxalic acid ammonium salt mixes in first organic solvent with BFEE with mol ratio, under 10～120 ℃ of conditions, reacts, and obtains difluoro oxalate ammonium borate class ionogen.
2. preparation method according to claim 1 is characterized in that, also comprises:
The difluoro oxalate ammonium borate class ionogen heating that step c) obtains step b), first organic solvent is removed in evaporation;
The product that step d) obtains step c) is used second organic solvent dissolution; Stir; Filter, remove second organic solvent, said second organic solvent is any one or two kinds in alcohol compound, nitrile compounds, compound fragrant hydrocarbon, ester compound and the ketone compounds.
3. preparation method according to claim 1; It is characterized in that said second organic solvent is that volume ratio is that 1: 1～5 alcohol compound and nitrile compounds, volume ratio are that 2～3: 1 alcohol compound and compound fragrant hydrocarbon, volume ratio are that 1～3: 1 alcohol compound and ketone compounds, volume ratio are that 1～3: 1 nitrile compounds and ketone compounds, volume ratio are that 3～6: 1 nitrile compounds and compound fragrant hydrocarbon, volume ratio are that 1～4: 1 ester compound and compound fragrant hydrocarbon, volume ratio are that 2～6: 1 ester compound and nitrile compounds, volume ratio are that 1: 1～3 ester compound and ketone compounds, volume ratio are that 2～6: 1 ketone compounds and compound fragrant hydrocarbon or volume ratio are 1: 1～3 alcohol compound and ester compound.
4. preparation method according to claim 1 is characterized in that, said step a) is specially:
Be that 0.9～1.1: 1.9～2.1 quaternary ammonium hydroxide mixes with oxalic acid with mol ratio, stir, be heated to, reacted 1～3 hour, be heated to 70～80 ℃ then, obtain the oxalic acid ammonium salt at 50～65 ℃.
5. preparation method according to claim 1 is characterized in that, said quaternary ammonium hydroxide is TMAH, tetraethyl ammonium hydroxide or TBAH.
6. preparation method according to claim 1 is characterized in that, the reaction times is 2～120 hours in the said step b).
7. the electrolytelike method of purification of difluoro oxalate ammonium borate is characterized in that, comprising:
Difluoro oxalate ammonium borate class ionogen to be purified is carried out crystallization with solvent, and suction filtration, said solvent are any three kinds in alcohol compound, nitrile compounds, compound fragrant hydrocarbon, ester compound and the ketone compounds;
Product recrystallization, drying that suction filtration is obtained.
8. method of purification according to claim 7 is characterized in that, said solvent is that volume ratio is 2: 1: 2 acetonitrile, toluene and an acetone; Volume ratio is 2: 1: 2 acetonitrile, diethyl carbonate and an acetone; Volume ratio is 3: 1: 1 acetonitrile, toluene and an acetone; Volume ratio is 3: 1: 1 acetonitrile, acetone and a methylcarbonate; Volume ratio is 4: 1: 1 acetonitrile, toluene and a diethyl carbonate; Volume ratio is 3: 1: 1 acetonitrile, 2-butanone and a methylcarbonate; Volume ratio is 1: 1: 1 acetonitrile, 2-butanone and a methyl alcohol; Volume ratio is acetonitrile, Virahol and the acetone that 1: 1: 2 acetonitrile, Virahol and methyl alcohol or volume ratio is 2: 1: 2.
9. method of purification according to claim 7 is characterized in that, said crystalline temperature is-50～5 ℃.
10. difluoro oxalate ammonium borate class ionogen has suc as formula the structure shown in the I:
The formula I,
Wherein, R
1, R
2, R
3And R
4Be alkyl independently separately.
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Cited By (5)
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| CN103483367A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Preparing method of difluoro oxalic acid boric acid metal salt |
| CN104681301A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super capacitor |
| CN109071568A (en) * | 2016-02-05 | 2018-12-21 | 国轩高科美国研究院 | The preparation of difluoro chelating borate |
| CN110041191A (en) * | 2019-04-30 | 2019-07-23 | 湖南九典宏阳制药有限公司 | A kind of purification process of pelubiprofen |
| CN112593078A (en) * | 2020-12-03 | 2021-04-02 | 江西理工大学 | Synthetic method of organic quaternary ammonium salt |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483367A (en) * | 2013-09-17 | 2014-01-01 | 上海璞泰来新材料技术有限公司 | Preparing method of difluoro oxalic acid boric acid metal salt |
| CN103483367B (en) * | 2013-09-17 | 2016-03-23 | 东莞市凯欣电池材料有限公司 | The preparation method of difluoro oxalic acid boric acid metal salt |
| CN104681301A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院长春应用化学研究所 | Organic electrolyte and asymmetric super capacitor |
| CN109071568A (en) * | 2016-02-05 | 2018-12-21 | 国轩高科美国研究院 | The preparation of difluoro chelating borate |
| CN110041191A (en) * | 2019-04-30 | 2019-07-23 | 湖南九典宏阳制药有限公司 | A kind of purification process of pelubiprofen |
| CN112593078A (en) * | 2020-12-03 | 2021-04-02 | 江西理工大学 | Synthetic method of organic quaternary ammonium salt |
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