CN102227034B - Lithium-air battery mixed type ionic liquid electrolyte and its preparation method - Google Patents
Lithium-air battery mixed type ionic liquid electrolyte and its preparation method Download PDFInfo
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- CN102227034B CN102227034B CN201110126277.5A CN201110126277A CN102227034B CN 102227034 B CN102227034 B CN 102227034B CN 201110126277 A CN201110126277 A CN 201110126277A CN 102227034 B CN102227034 B CN 102227034B
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Abstract
The invention discloses a lithium-air battery mixed type ionic liquid electrolyte and its preparation method, which belongs to the electrolyte preparation technology field. The electrolyte can be obtained by mixing dialkyl pyridines hexafluorophosphate ionic liquid, organic lithium salt with hexafluorophosphoric acid double core annular quaternary ammonium salt under the protective atmosphere of argon, stirring in the vacuum environment and vacuum drying. The electrolyte has the advantages of wide electrochemistry window, high conductivity, small internal resistance and excellent hydrophobicity. The specific capacitance and charge and discharge frequency can be improved by the lithium-air battery produced by the electrolyte, so that the electrolyte has strong practicality and enables large-scale industrial production.
Description
Technical field
The invention belongs to the electrolyte preparing technical field, be specifically related to a kind of ionic liquid electrolyte of the mixed type for lithium-air battery and preparation method thereof.
Background technology
The physicochemical properties that ionic liquid is good with it, as desirable " green " solvent, novel reaction medium and " soft " functional material, become multidisciplinary intersection, one of most active Green Chemistry research frontier.The chemical property of ionic liquid excellence, make it in the electrochemical research field, have high application potential.The theoretical specific capacity that lithium-air battery is high with it and specific energy and the characteristic such as environmentally friendly and become the power conversion system received much concern at present.Its cathode active material O
2can directly from surrounding air, obtain, due to the high theoretical specific capacity of Li (3862mAh/g), make the theoretical specific energy of lithium-air battery can reach 11,140Wh/kg simultaneously, this theoretical specific energy, higher than the power supply system of current all routines, is more than 10 times of current high performance lithium ion battery.The principal element that determines the lithium-air battery performance is electrolyte and electrode, and that ionic liquid has an electrochemical window is broad, non-volatile, the advantage such as easily store and recycle, novel ion liquid is applied in the electrolyte research of lithium-air battery, become the research forward position of current multidisciplinary intersection, correlative study is in the ascendant.
For organic electrolyte system, owing in preparation, having used organic solvent, and organic solvent is due to the corrosion that contains water and can cause the negative pole lithium, causes the specific capacity of lithium-air battery to descend and efficiency for charge-discharge reduces.Solid electrolyte and gel electrolyte good reliability and not there will be electrolyte leakage, specific energy is high, cyclical voltage is wider, but under room temperature the electrolytical conductivity of most solid and solubility lower.And the mixed type ionic liquid electrolyte has many excellent properties, the ionic liquid that design as ionic liquid by zwitterion can prepare hydrophobic type is to alleviate reacting from airborne water and lithium metal, and the thermal stability of hexafluorophosphoric acid double-core ring-type quaternary ammonium salt can prevent that volatilize the in the course of the work battery capacity that causes of electrolyte from descending etc., these all are enough to make it to have the potentiality that become lithium-air battery electrolyte.
Summary of the invention
The object of the present invention is to provide a kind of mixed type ionic liquid electrolyte.
The present invention also aims to provide a kind of preparation method of mixed type ionic liquid electrolyte.
The present invention also aims to provide the application of a kind of mixed type ionic liquid electrolyte in lithium-air battery.
A kind of mixed type ionic liquid electrolyte, this electrolyte is comprised of dialkyl group pyridines hexafluorophosphate ionic liquid, organic lithium salt and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt.
Described dialkyl group pyridines hexafluorophosphate ionic liquid is 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid or 1-ethyl-3-ethylpyridine hexafluorophosphate ionic liquid; Organic lithium salt is lithium hexafluoro phosphate, lithium perchlorate or LiBF4; Hexafluorophosphoric acid double-core ring-type quaternary ammonium salt is N, N '-1-ethyl-4-butyl triethylene diammonium hexafluorophosphate or N, N '-1-ethyl-4-ethyl triethylene diammonium hexafluorophosphate.
Described dialkyl group pyridines hexafluorophosphate ionic liquid is 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid; Organic lithium salt is lithium hexafluoro phosphate; The mol ratio of 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid, lithium hexafluoro phosphate and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt is 5: 4: 1,5: 3: 2,4: 4: 2,3: 5: 2,4: 5: 1.
A kind of preparation method of mixed type ionic liquid electrolyte; at first prepare dialkyl group pyridines hexafluorophosphate ionic liquid and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt; then under argon shield atmosphere; dialkyl group pyridines hexafluorophosphate ionic liquid is mixed with organic lithium salt and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt; uniform stirring 36h under vacuum environment; by vacuumize 24h, obtain.
The preparation method of described dialkyl group pyridines hexafluorophosphate ionic liquid is:
Step 1: 100～500ml N-picoline and mol ratio are slightly larger than to 1 respective volume bromination of n-butane and join in 2000ml single port flask, perhaps 100～500ml N-ethylpyridine and mol ratio being slightly larger than to 1 respective volume bromic ether joins in 2000ml single port flask, in 100 ℃ of lower oil baths of temperature, reflux, after backflow 36h, decrease temperature crystalline;
Step 2: the prepared crystallization of step 1 is carried out to suction filtration;
Step 3: add 60～300ml acetonitrile and 120～600ml ethyl acetate in the crystal obtained to the step 2 suction filtration, heat under 80 ℃ of oil baths, backflow 20min, treat that white precipitate dissolves fully, filters while hot decrease temperature crystalline;
Step 4: obtain white crystal after the operation of repeating step two and step 3 2～3 times, i.e. intermediate;
Step 5: get intermediate 43.8～219.0 grams that step 4 makes, be put in the 1000ml beaker, add 100～500ml deionized water and stirring that it is fully dissolved;
Step 6: get ammonium hexafluorophosphate 32.6～163.0 grams, add in the described beaker of step 5, stir 4 hours under room temperature;
Step 7: the reactant liquor obtained through step 6 by deionized water and each washed twice of ether for 20～100ml, is removed water layer respectively;
Step 8: the solution that step 7 is obtained, 80 ℃ of vacuum dryings 32 hours, obtains dialkyl group pyridines hexafluorophosphate ionic liquid.
The preparation method of described hexafluorophosphoric acid double-core ring-type quaternary ammonium salt is:
Step 1: N, the preparation of N '-1-ethyl-4-butyl triethylene diammonium halogeno salt, by C
2h
5br is added drop-wise in the methanol solution of triethylene diammonium, adds hot reflux, and unreacted raw material is removed in decompression distillation, makes monosubstituted N-1-base triethylene diammonium bromo salt;
Step 2: monosubstituted N-1-base triethylene diammonium bromo salt and mol ratio are slightly larger than to the C of 1: 1
4h
9br or C
2h
5the Br wiring solution-forming, continue to add hot reflux, preparation N, N '-1-ethyl-4 butyl triethylene diammonium bromo salt or N, N '-1-ethyl-4 ethyl triethylene diammonium bromo salt;
Step 3: by the N made, N '-1,4-diethyl triethylene diammonium bromine salt or N, N '-1-ethyl-4 ethyl triethylene diammonium bromo salt is dissolved in a small amount of water, join etc. in the hexafluorophosphoric acid aqueous solution of molal weight, carry out ion-exchange, obtain hexafluorophosphoric acid double-core ring-type quaternary ammonium salt after the decompression distillation recrystallization, then crude salt is dissolved in appropriate solvent, add decolorizer and add hot reflux, after reaction finishes, material is filtered while hot, static crystallization, obtain the hexafluorophosphoric acid double-core ring-type quaternary ammonium salt of finished product.
A kind of mixed type ionic liquid electrolyte is for lithium-air battery, and lithium-air battery comprises cathode of lithium, electrolyte, air positive pole and seal casinghousing.
Beneficial effect of the present invention: electrolyte of the present invention has the advantages such as electrochemical window is broad, conductivity is higher, internal resistance is less, and hydrophobic performance excellence, add hexafluorophosphoric acid double-core ring-type quaternary ammonium salt, can utilize its thermal stability to prevent the battery capacity decline that electrolyte volatilizees in the course of the work and causes, the lithium-air battery that electrolyte is made has improved the specific capacity of battery and has discharged and recharged number of times, practical, but large-scale industrial production.
Embodiment
Below with specific embodiment, the present invention will be further described.
The preparation of embodiment 1 dialkyl group pyridines hexafluorophosphate ionic liquid
Step 1: 100～500ml N-picoline and mol ratio are slightly larger than to 1 respective volume bromination of n-butane and join in 2000ml single port flask, perhaps 100～500ml N-ethylpyridine and mol ratio being slightly larger than to 1 respective volume bromic ether joins in 2000ml single port flask, in 100 ℃ of lower oil baths of temperature, reflux, after backflow 36h, decrease temperature crystalline;
Step 2: the prepared crystallization of step 1 is carried out to suction filtration;
Step 3: add 60～300ml acetonitrile and 120～600ml ethyl acetate in the crystal obtained to the step 2 suction filtration, heat under 80 ℃ of oil baths, backflow 20min, treat that white precipitate dissolves fully, filters while hot decrease temperature crystalline;
Step 4: obtain white crystal after the operation of repeating step two and step 3 2～3 times, i.e. intermediate;
Step 5: get intermediate 43.8～219.0 grams that step 4 makes, be put in the 1000ml beaker, add 100～500ml deionized water and stirring that it is fully dissolved;
Step 6: get ammonium hexafluorophosphate 32.6～163.0 grams, add in the described beaker of step 5, stir 4 hours under room temperature;
Step 7: the reactant liquor obtained through step 6 by deionized water and each washed twice of ether for 20～100ml, is removed water layer respectively;
Step 8: the solution that step 7 is obtained, 80 ℃ of vacuum dryings 32 hours, obtains dialkyl group pyridines hexafluorophosphate ionic liquid.
The preparation of embodiment 2 hexafluorophosphoric acid double-core ring-type quaternary ammonium salts
Step 1: N, the preparation of N '-1-ethyl-4-butyl triethylene diammonium halogeno salt, by C
2h
5br is added drop-wise in the methanol solution of triethylene diammonium, adds hot reflux, and unreacted raw material is removed in decompression distillation, makes monosubstituted N-1-base triethylene diammonium bromo salt;
Step 2: monosubstituted N-1-base triethylene diammonium bromo salt and mol ratio are slightly larger than to the C of 1: 1
4h
9br or C
2h
5the Br wiring solution-forming, continue to add hot reflux, preparation N, N '-1-ethyl-4 butyl triethylene diammonium bromo salt or N, N '-1-ethyl-4 ethyl triethylene diammonium bromo salt;
Step 3: by the N made, N '-1,4-diethyl triethylene diammonium bromine salt or N, N '-1-ethyl-4 ethyl triethylene diammonium bromo salt is dissolved in a small amount of water, join etc. in the hexafluorophosphoric acid aqueous solution of molal weight, carry out ion-exchange, obtain hexafluorophosphoric acid double-core ring-type quaternary ammonium salt after the decompression distillation recrystallization, then crude salt is dissolved in appropriate solvent, add decolorizer and add hot reflux, after reaction finishes, material is filtered while hot, static crystallization, obtain the hexafluorophosphoric acid double-core ring-type quaternary ammonium salt of finished product.
The preparation of embodiment 3 mixed type ionic liquid electrolytes
(1) under argon shield atmosphere; by 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid and lithium hexafluoro phosphate and N; N '-1-ethyl-4-butyl triethylene diammonium hexafluorophosphate mixes; 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid, lithium hexafluoro phosphate and N; the mol ratio of N '-1-ethyl-4-butyl triethylene diammonium hexafluorophosphate is 5: 4: 1,5: 3: 2,4: 4: 2,3: 5: 2 or 4: 5: 1; uniform stirring 36h under vacuum environment; by vacuumize 24h, obtain.
(2) under argon shield atmosphere; by 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid and lithium hexafluoro phosphate and N; N '-1-ethyl-4-ethyl triethylene diammonium hexafluorophosphate mixes; 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid, lithium hexafluoro phosphate and N; the mol ratio of N '-1-ethyl-4-ethyl triethylene diammonium hexafluorophosphate is 5: 4: 1,5: 3: 2,4: 4: 2,3: 5: 2 or 4: 5: 1; uniform stirring 36h under vacuum environment; by vacuumize 24h, obtain.
(3) under argon shield atmosphere; by 1-ethyl-3-ethylpyridine hexafluorophosphate ionic liquid and lithium perchlorate and N, N '-1-ethyl-4-ethyl triethylene diammonium hexafluorophosphate mixes, uniform stirring 36h under vacuum environment; by vacuumize 24h, obtain.
(4) under argon shield atmosphere; by 1-ethyl-3-ethylpyridine hexafluorophosphate ionic liquid and LiBF4 and N, N '-1-ethyl-4-ethyl triethylene diammonium hexafluorophosphate mixes, uniform stirring 36h under vacuum environment; by vacuumize 24h, obtain.
(5) under argon shield atmosphere; by 1-ethyl-3-ethylpyridine hexafluorophosphate ionic liquid and LiBF4 and N, N '-1-ethyl-4-butyl triethylene diammonium hexafluorophosphate mixes, uniform stirring 36h under vacuum environment; by vacuumize 24h, obtain.
(6) under argon shield atmosphere; by 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid and lithium perchlorate and N, N '-1-ethyl-4-butyl triethylene diammonium hexafluorophosphate mixes, uniform stirring 36h under vacuum environment; by vacuumize 24h, obtain.
The assembling of embodiment 4 lithium-air batteries
The described mixed type ionic liquid electrolyte of embodiment 3 is placed in the middle of cathode of lithium and air positive pole, by seal casinghousing, is assembled into lithium-air battery.
Claims (5)
1. a mixed type ionic liquid electrolyte, is characterized in that, this electrolyte is comprised of dialkyl group pyridines hexafluorophosphate ionic liquid, organic lithium salt and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt;
Described dialkyl group pyridines hexafluorophosphate ionic liquid is 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid, described organic lithium salt is lithium hexafluoro phosphate, and the mol ratio of described 1-methyl-3-butyl-pyridinium hexafluorophosphate ionic liquid, lithium hexafluoro phosphate and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt is 5:4:1,5:3:2,4:4:2,3:5:2,4:5:1.
2. the preparation method of a kind of mixed type ionic liquid electrolyte as claimed in claim 1; it is characterized in that; at first prepare dialkyl group pyridines hexafluorophosphate ionic liquid and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt; then under argon shield atmosphere; dialkyl group pyridines hexafluorophosphate ionic liquid is mixed with organic lithium salt and hexafluorophosphoric acid double-core ring-type quaternary ammonium salt; uniform stirring 36h under vacuum environment, by vacuumize 24h, obtain.
3. a kind of preparation method of mixed type ionic liquid electrolyte according to claim 2, is characterized in that, the preparation method of described dialkyl group pyridines hexafluorophosphate ionic liquid is:
Step 1: 100～500ml N-picoline and mol ratio are slightly larger than to 1 respective volume bromination of n-butane and join in 2000ml single port flask, perhaps 100～500ml N-ethylpyridine and mol ratio being slightly larger than to 1 respective volume bromic ether joins in 2000ml single port flask, in 100 ℃ of lower oil baths of temperature, reflux, after backflow 36h, decrease temperature crystalline;
Step 2: the prepared crystallization of step 1 is carried out to suction filtration;
Step 3: add 60～300ml acetonitrile and 120～600ml ethyl acetate in the crystal obtained to the step 2 suction filtration, heat under 80 ℃ of oil baths, backflow 20min, treat that white precipitate dissolves fully, filters while hot decrease temperature crystalline;
Step 4: obtain white crystal after the operation of repeating step two and step 3 2～3 times, i.e. intermediate;
Step 5: get intermediate 43.8～219.0 grams that step 4 makes, be put in the 1000ml beaker, add 100～500ml deionized water and stirring that it is fully dissolved;
Step 6: get ammonium hexafluorophosphate 32.6～163.0 grams, add in the described beaker of step 5, stir 4 hours under room temperature;
Step 7: the reactant liquor obtained through step 6 by deionized water and each washed twice of ether for 20～100ml, is removed water layer respectively;
Step 8: the solution that step 7 is obtained, 80 ℃ of vacuum dryings 32 hours, obtains dialkyl group pyridines hexafluorophosphate ionic liquid.
4. a kind of preparation method of mixed type ionic liquid electrolyte according to claim 2, is characterized in that, the preparation method of described hexafluorophosphoric acid double-core ring-type quaternary ammonium salt is:
Step 1: N, the preparation of N '-1-ethyl-4-butyl triethylene diammonium halogeno salt, by C
2h
5br is added drop-wise in the methanol solution of triethylene diammonium, adds hot reflux, and unreacted raw material is removed in decompression distillation, makes monosubstituted N-1-base triethylene diammonium bromo salt;
Step 2: the C that monosubstituted N-1-base triethylene diammonium bromo salt and mol ratio is slightly larger than to 1:1
4h
9br or C
2h
5the Br wiring solution-forming, continue to add hot reflux, preparation N, N '-1-ethyl-4 butyl triethylene diammonium bromo salt or N, N '-1-ethyl-4 ethyl triethylene diammonium bromo salt;
Step 3: by the N made, N ’ – 1,4 – diethyl triethylene diammonium bromine salt or N, N '-1-ethyl-4 ethyl triethylene diammonium bromo salt is dissolved in a small amount of water, join etc. in the hexafluorophosphoric acid aqueous solution of molal weight, carry out ion-exchange, obtain hexafluorophosphoric acid double-core ring-type quaternary ammonium salt after the decompression distillation recrystallization, then crude salt is dissolved in appropriate solvent, add decolorizer and add hot reflux, after reaction finishes, material is filtered while hot, static crystallization, obtain the hexafluorophosphoric acid double-core ring-type quaternary ammonium salt of finished product.
5. the application of the described mixed type ionic liquid electrolyte of claim 1, is characterized in that, this electrolyte is for lithium-air battery, and lithium-air battery comprises cathode of lithium, electrolyte, air positive pole and seal casinghousing.
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