CN104193685A - Preparing method of thiocyanate functionalized ionic liquid electrolyte - Google Patents
Preparing method of thiocyanate functionalized ionic liquid electrolyte Download PDFInfo
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- CN104193685A CN104193685A CN201410244496.7A CN201410244496A CN104193685A CN 104193685 A CN104193685 A CN 104193685A CN 201410244496 A CN201410244496 A CN 201410244496A CN 104193685 A CN104193685 A CN 104193685A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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Abstract
A preparing method of a thiocyanate functionalized ionic liquid electrolyte is provided. The method includes: under the protection of a nitrogen atmosphere, mixing an amine or phosphorus monomer and a halogenated alkyl hydrocarbon, heating, refluxing, cooling, drying under vacuum to obtain a halogenated ionic liquid intermediate, adding sodium thiocyanate into the halogenated ionic liquid intermediate, mixing, removing precipitate and a sodium salt respectively by using an acetone solvent and a dichloromethane organic solvent, performing rotary evaporation to remove the acetone solvent and the dichloromethane organic solvent, heating the obtained mixed solution, and drying under vacuum to obtain the thiocyanate functionalized ionic liquid. A room-temperature melt salt comprising an organic cation and the thiocyanate anion, which is synthesized by a two-step synthesis method, is adopted as the electrolyte. The method is characterized by simple operation, low cost, low equipment requirements and capability of large-scale production. The electrolyte is characterized by being non-volatile, non-flammable, low in viscosity, high in conductivity, and adjustable.
Description
Technical field
The present invention relates to Ionic liquids technologies field, particularly a kind of preparation method of thiocyanate ion functionalized ion liquid electrolytic solution.
Background technology
Society, the global problem-energy storage being caused by the burning of fossil oil, global warming etc.Developed at present, social environment close friend's energy storage technology is had to solar cell in photovoltaic industry, lithium ion battery and ultracapacitor.Ultracapacitor is the new forms of energy energy storage device between traditional capacitor and chemical energy storage battery.The features such as ultracapacitor has that specific power density is high, the time that discharges and recharges is short, has extended cycle life, power storage time length, memoryless function.Because the specific energy density specific power density low, lithium ion battery of traditional capacitor is low, in application aspect such as superpower and high impulses, ultracapacitor becomes the focus of research.
Electrolytic solution, " blood " of electrical condenser, is playing an important role aspect heavy-current discharge and energy density.Yet, concerning ultracapacitor, square being directly proportional of the operating voltage that its energy density determines to electrolytic solution.Yet, the shortcoming such as the operating voltage of aqueous electrolyte can not surpass 1V, and has corrodibility, volatile; Organic electrolyte has inflammable shortcoming; The viscosity of ionic liquid [Bmim] BF4 that is usually used in electrolytic solution is large, and specific conductivity is little, and its specific conductivity is only at room temperature 2.94mS/cm.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of thiocyanate ion functionalized ion liquid electrolytic solution, present method is simple to operate, be convenient to realize, the thiocyanate ion liquid vapors of preparation forces down, and has the feature of non-volatile, non-inflammability, low viscosity, high conductivity, adjustability.
In order to achieve the above object, the technical scheme that the present invention takes is:
A preparation method for thiocyanate ion functionalized ion liquid electrolytic solution, comprising:
Step 1: under nitrogen environment protection, get amine or Phosphorus monomer joins in flask, in flask, drip haloalkyl hydrocarbon, dropwise and rear mixture in flask is heated, 4-10h again refluxes after being warming up to 60-110 ℃, after finishing, reaction is cooled to room temperature, with organic solvent washing, remove unreacted material 3 times again, rotary evaporation is removed organic solvent, product obtained above is heated to be decompressed to 0.1MPa vacuum-drying 8-12h at 60-80 ℃, obtains halogenation ionic liquid intermediate;
Step 2: halogenation ionic liquid intermediate and the Sodium Thiocyanate 99 (NaSCN) of getting above-mentioned preparation, ratio according to mol ratio 1:1-1:5 is mixed, after mixing, adding molar weight is in Sodium Thiocyanate 99 2-10 acetone solvent doubly, magnetic agitation 12-72h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be Sodium Thiocyanate 99 2-10 methylene dichloride organic solvent doubly again, magnetic agitation 1-5h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 60-80 ℃ 0.1MPa vacuum-drying 8-12h, the final thiocyanate ion liquid that obtains.
Add described amine in flask or the mol ratio 1:5 of Phosphorus monomer and haloalkyl hydrocarbon.
Described amine or Phosphorus monomer comprise: N-Methylimidazole.
Described haloalkyl hydrocarbon comprises: bromo hexane, n-propyl bromide and bromination of n-butane.
Described organic solvent is the solvent that ratio that acetoneand ethyl acetate is 1:1-1:5 according to mol ratio is mixed.
Described halogenation ionic liquid intermediate is comprised of X positively charged ion and Y negatively charged ion, and its general formula is: [X] Y, described Y negatively charged ion comprises: F
-, Cl
-, Br
-and I
-, described X positively charged ion comprises: alkyl imidazolium cation, pyroles positively charged ion, pyrrolidines positively charged ion, pyridines positively charged ion, piperidines positively charged ion, quaternary amines positively charged ion or quaternary phosphonium cationoid,
Described alkyl imidazolium cation, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 0-12 carbon atom, and R
2for containing the saturated or undersaturated alkyl of 1-25 carbon atom;
Described pyroles positively charged ion, structure is as follows: (having added one)
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom.
Described pyrrolidines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom.
Described pyridines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom;
Described piperidines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom;
Described quaternary amines positively charged ion, structure is as follows:
R in formula
1, R
2, R
3, R
4for containing the saturated or undersaturated alkyl of 1-25 carbon atom;
Described quaternary phosphonium cationoid, structure is as follows:
R in formula
1, R
2, R
3, R
4, R
5, R
6for containing the saturated or undersaturated alkyl of 1-25 carbon atom.
Described halogenation ionic liquid intermediate comprises: 1-ethyl-3-methylimidazole bromine salt (EmimBr), 1-propyl group-3-Methylimidazole bromine salt (PmimBr) or 1-butyl-3-Methylimidazole bromine salt (BmimBr).
Described thiocyanate ion liquid is by thiocyanate ion negatively charged ion and cation composition, and described positively charged ion comprises: imidazoles, pyrroles, tetramethyleneimine, pyridine, piperidines, quaternary ammonium salt or quaternary alkylphosphonium salt.
Beneficial effect of the present invention is:
The present invention utilizes the synthetic room temperature melting salt being comprised of organic cation and thiocyanate ion negatively charged ion of two step synthesis methods as electrolytic solution, has simple to operately, with low cost, and equipment requirements is low, and feature can be mass-produced.Electrolytic solution prepared by the present invention, has the feature of non-volatile, non-inflammability, low viscosity, high conductivity, adjustability.
Accompanying drawing explanation
Fig. 1 is the graph of a relation of embodiment 5 intermediate ion liquid electrolyte specific conductivity and temperature.
Fig. 2 is the cyclic voltammetry curve of embodiment 5 intermediate ion liquid electrolyte.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail.
The present invention is a kind of preparation method of thiocyanate ion functionalized ion liquid electrolytic solution, comprising:
Step 1: under nitrogen environment protection, get amine or Phosphorus monomer joins in flask, in flask, drip haloalkyl hydrocarbon, dropwise and rear mixture in flask is heated, 4-10h again refluxes after being warming up to 60-110 ℃, after finishing, reaction is cooled to room temperature, with organic solvent washing, remove unreacted material 3 times again, rotary evaporation is removed organic solvent, product obtained above is heated to be decompressed to 0.1MPa vacuum-drying 8-12h at 60-80 ℃, obtains halogenation ionic liquid intermediate;
Step 2: halogenation ionic liquid intermediate and the Sodium Thiocyanate 99 (NaSCN) of getting above-mentioned preparation, ratio according to mol ratio 1:1-1:5 is mixed, after mixing, adding molar weight is in Sodium Thiocyanate 99 2-10 acetone solvent doubly, magnetic agitation 12-72h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be Sodium Thiocyanate 99 2-10 methylene dichloride organic solvent doubly again, magnetic agitation 1-5h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 60-80 ℃ 0.1MPa vacuum-drying 8-12h, the final thiocyanate ion liquid that obtains.
Add described amine in flask or the mol ratio 1:5 of Phosphorus monomer and haloalkyl hydrocarbon.
Described amine or Phosphorus monomer comprise: N-Methylimidazole.
Described haloalkyl hydrocarbon comprises: bromo hexane, n-propyl bromide or bromination of n-butane.
Described organic solvent is the solvent that ratio that acetoneand ethyl acetate is 1:1-1:5 according to mol ratio is mixed.
Described halogenation ionic liquid intermediate is comprised of X positively charged ion and Y negatively charged ion, and its general formula is: [X] Y, described Y negatively charged ion comprises: F
-, Cl
-, Br
-and I
-, described X positively charged ion comprises: alkyl imidazolium cation, pyroles positively charged ion, pyrrolidines positively charged ion, pyridines positively charged ion, piperidines positively charged ion, quaternary amines positively charged ion and quaternary phosphonium cationoid,
Described alkyl imidazolium cation, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 0-12 carbon atom, and R
2for containing the saturated or undersaturated alkyl of 1-25 carbon atom;
Described pyroles positively charged ion, structure is as follows: (having added one)
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom.
Described pyrrolidines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom.
Described pyridines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom;
Described piperidines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom;
Described quaternary amines positively charged ion, structure is as follows:
R in formula
1, R
2, R
3, R
4for containing the saturated or undersaturated alkyl of 1-25 carbon atom;
Described quaternary phosphonium cationoid, structure is as follows:
R in formula
1, R
2, R
3, R
4, R
5, R
6for containing the saturated or undersaturated alkyl of 1-25 carbon atom.
Described halogenation ionic liquid intermediate comprises: 1-ethyl-3-methylimidazole bromine salt (EmimBr), 1-propyl group-3-Methylimidazole bromine salt (PmimBr) or 1-butyl-3-Methylimidazole bromine salt (BmimBr).
Described thiocyanate ion liquid is by thiocyanate ion negatively charged ion and cation composition, and described positively charged ion comprises: imidazoles, pyrroles, tetramethyleneimine, pyridine, piperidines, quaternary ammonium salt or quaternary alkylphosphonium salt.
Embodiment 1:
Under nitrogen environment protection, the ratio that is 1:1 with bromo hexane according to mol ratio by N-Methylimidazole joins in flask mixes, and mixture is warming up to 60 ℃ of 4h that reflux again afterwards, after reaction finishes, is chilled to room temperature, obtains white crystal.The organic solvent that the ratio that to use by acetoneand ethyl acetate be 1:1-1:5 according to mol ratio again mixes is to white crystal washing 3 times, remove unreacted material, then rotary evaporation is removed organic solvent, the white crystal obtaining is heated to be decompressed at 60 ℃ 0.1MPa vacuum-drying 10h, obtain white solid, be halogenation ionic liquid intermediate 1-ethyl-3-methylimidazole bromine salt (EmimBr), productive rate is 91%.
The ratio that is 1:2 according to mol ratio by 1-ethyl-3-methylimidazole bromine salt and Sodium Thiocyanate 99 (NaSCN) is mixed, after mixing, adding molar weight is in the acetone solvent of 5 times of Sodium Thiocyanate 99s, magnetic agitation 72h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be the methylene dichloride organic solvent of 3 times of Sodium Thiocyanate 99s again, magnetic agitation 1h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 60 ℃ 0.1MPa vacuum-drying 10h, the final thiocyanate ion liquid 1-ethyl-3-methylimidazole thiocyanate-(EmimSCN) that obtains, productive rate is 79%.
Embodiment 2:
Under nitrogen environment protection, the ratio that is 1:1 with bromo hexane according to mol ratio by N-Methylimidazole joins in flask mixes, and mixture is warming up to 60 ℃ of 10h that reflux again afterwards, after reaction finishes, is chilled to room temperature, obtains white crystal.The organic solvent that the ratio that to use by acetoneand ethyl acetate be 1:1-1:5 according to mol ratio again mixes is to white crystal washing 3 times, remove unreacted material, then rotary evaporation is removed organic solvent, the white crystal obtaining is heated to be decompressed at 60 ℃ 0.1MPa vacuum-drying 10h, obtain white solid, be halogenation ionic liquid intermediate 1-ethyl-3-methylimidazole bromine salt (EmimBr), productive rate is 94%.
The ratio that is 1:2 according to mol ratio by 1-ethyl-3-methylimidazole bromine salt and Sodium Thiocyanate 99 is mixed, after mixing, adding molar weight is in the acetone solvent of 5 times of Sodium Thiocyanate 99s, magnetic agitation 72h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be the methylene dichloride organic solvent of 3 times of Sodium Thiocyanate 99s again, magnetic agitation 1h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 60 ℃ 0.1MPa vacuum-drying 10h, the final thiocyanate ion liquid 1-ethyl-3-methylimidazole thiocyanate-(EmimSCN) that obtains, productive rate is 77%.
Embodiment 3:
Under nitrogen environment protection, the ratio that is 1:1.1 with n-propyl bromide according to mol ratio by N-Methylimidazole joins in flask mixes, and mixture is warming up to 80 ℃ of 10h that reflux again afterwards, after reaction finishes, is chilled to room temperature, obtains light yellow liquid.The organic solvent that the ratio that to use by acetoneand ethyl acetate be 1:1-1:5 according to mol ratio again mixes is to light yellow liquid washing 3 times, remove unreacted material (because organic solvent and product are immiscible, this mode of washing, for adding glass stick after organic solvent to stir for a moment, is outwelled organic solvent.), then rotary evaporation is removed organic solvent, and the light yellow liquid obtaining is heated to be decompressed at 70 ℃ 0.1MPa vacuum-drying 10h, obtain light yellow liquid (because the fusing point of ionic liquid itself is low, even if be called salt, but state is liquid, and different substances fusing point is different.), i.e. halogenation ionic liquid intermediate 1-propyl group-3-Methylimidazole bromine salt (PmimBr), productive rate is 95%.
The ratio that is 1:1 according to mol ratio by 1-propyl group-3-Methylimidazole bromine salt and Sodium Thiocyanate 99 is mixed, after mixing, adding molar weight is in the acetone solvent of 3 times of Sodium Thiocyanate 99s, magnetic agitation 48h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be the methylene dichloride organic solvent of 2 times of Sodium Thiocyanate 99s again, magnetic agitation 1h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 70 ℃ 0.1MPa vacuum-drying 10h, the final thiocyanate ion liquid 1-propyl group-3-Methylimidazole thiocyanate-(PmimSCN) that obtains, productive rate is 81%.
Embodiment 4:
Under nitrogen environment protection, the ratio that is 1:1.1 with n-propyl bromide according to mol ratio by N-Methylimidazole joins in flask mixes, and mixture is warming up to 80 ℃ of 10h that reflux again afterwards, after reaction finishes, is chilled to room temperature, obtains light yellow liquid.The organic solvent that the ratio that to use by acetoneand ethyl acetate be 1:1-1:5 according to mol ratio again mixes is to light yellow liquid washing 3 times, remove unreacted material (because organic solvent and product are immiscible, this mode of washing, for adding glass stick after organic solvent to stir for a moment, is outwelled organic solvent.), then rotary evaporation is removed organic solvent, and the light yellow liquid obtaining is heated to be decompressed at 70 ℃ 0.1MPa vacuum-drying 10h, obtain light yellow liquid (because the fusing point of ionic liquid itself is low, even if be called salt, but state is liquid, and different substances fusing point is different.), i.e. halogenation ionic liquid intermediate 1-propyl group-3-Methylimidazole bromine salt (PmimBr), productive rate is 94%.
The ratio that is 1:2 according to mol ratio by 1-propyl group-3-Methylimidazole bromine salt and Sodium Thiocyanate 99 is mixed, after mixing, adding molar weight is in the acetone solvent of 3 times of Sodium Thiocyanate 99s, magnetic agitation 48h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be the methylene dichloride organic solvent of 3 times of Sodium Thiocyanate 99s again, magnetic agitation 1h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 70 ℃ 0.1MPa vacuum-drying 10h, the final thiocyanate ion liquid 1-propyl group-3-Methylimidazole thiocyanate-(PmimSCN) that obtains, productive rate is 79%.
Embodiment 5:
Under nitrogen environment protection, the ratio that is 1:1.1 with bromination of n-butane according to mol ratio by N-Methylimidazole joins in flask mixes, and mixture is warming up to 80 ℃ of 10h that reflux again afterwards, after reaction finishes, is chilled to room temperature, obtains white crystal.The organic solvent that the ratio that to use by acetoneand ethyl acetate be 1:1-1:5 according to mol ratio again mixes is to white crystal washing 3 times, remove unreacted material, then rotary evaporation is removed organic solvent, the white crystal obtaining is heated to be decompressed at 80 ℃ 0.1MPa vacuum-drying 12h, obtain white solid, be halogenation ionic liquid intermediate 1-butyl-3-Methylimidazole bromine salt (BmimBr), productive rate is 92%.
The ratio that is 1:1.5 according to mol ratio by 1-butyl-3-Methylimidazole bromine salt and Sodium Thiocyanate 99 is mixed, after mixing, adding molar weight is in the acetone solvent of 5 times of Sodium Thiocyanate 99s, magnetic agitation 48h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be the methylene dichloride organic solvent of 2 times of Sodium Thiocyanate 99s again, magnetic agitation 1h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 80 ℃ 0.1MPa vacuum-drying 12h, the final thiocyanate ion liquid 1-butyl-3-Methylimidazole thiocyanate-(BmimSCN) that obtains, productive rate is 79%.
Embodiment 6:
Under nitrogen environment protection, the ratio that is 1:1.1 with bromination of n-butane according to mol ratio by N-Methylimidazole joins in flask mixes, and mixture is warming up to 110 ℃ of 8h that reflux again afterwards, after reaction finishes, is chilled to room temperature, obtains pale yellow crystals.The organic solvent that the ratio that to use by acetoneand ethyl acetate be 1:1-1:5 according to mol ratio again mixes is to pale yellow crystals washing 3 times, remove unreacted material, then rotary evaporation is removed organic solvent, the pale yellow crystals obtaining is heated to be decompressed at 80 ℃ 0.1MPa vacuum-drying 12h, obtain white solid, be halogenation ionic liquid intermediate 1-butyl-3-Methylimidazole bromine salt (BmimBr), productive rate is 94%.
The ratio that is 1:2 according to mol ratio by 1-butyl-3-Methylimidazole bromine salt and Sodium Thiocyanate 99 is mixed, after mixing, adding molar weight is in the acetone solvent of 5 times of Sodium Thiocyanate 99s, magnetic agitation 48h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be the methylene dichloride organic solvent of 3 times of Sodium Thiocyanate 99s again, magnetic agitation 2h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 80 ℃ 0.1MPa vacuum-drying 12h, the final thiocyanate ion liquid 1-butyl-3-Methylimidazole thiocyanate-(BmimSCN) that obtains, productive rate is 79%.
Embodiment 7:
Under nitrogen environment protection, the ratio that is 1:1.2 with bromination of n-butane according to mol ratio by N-Methylimidazole joins in flask mixes, and mixture is warming up to 110 ℃ of 8h that reflux again afterwards, after reaction finishes, is chilled to room temperature, obtains pale yellow crystals.The organic solvent that the ratio that to use by acetoneand ethyl acetate be 1:1-1:5 according to mol ratio again mixes is to pale yellow crystals washing 3 times, remove unreacted material, then rotary evaporation is removed organic solvent, the pale yellow crystals obtaining is heated to be decompressed at 80 ℃ 0.1MPa vacuum-drying 12h, obtain white solid, be halogenation ionic liquid intermediate 1-butyl-3-Methylimidazole bromine salt (BmimBr), productive rate is 95%.
The ratio that is 1:3 according to mol ratio by 1-butyl-3-Methylimidazole bromine salt and Sodium Thiocyanate 99 is mixed, after mixing, adding molar weight is in the acetone solvent of 5 times of Sodium Thiocyanate 99s, magnetic agitation 48h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be the methylene dichloride organic solvent of 3 times of Sodium Thiocyanate 99s again, magnetic agitation 1h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 80 ℃ 0.1MPa vacuum-drying 12h, the final thiocyanate ion liquid 1-butyl-3-Methylimidazole thiocyanate-(BmimSCN) that obtains, productive rate is 79%.
To make electrolytic solution containing thiocyanate ion liquid, form respectively ultracapacitor and lithium-ion battery system, and test its chemical property, comprising cyclic voltammetric (CV), alternating-current impedance (EIS), constant current charge-discharge (GCD), leakage current, cycle life etc.
To make electrolytic solution containing thiocyanate ion liquid, form lithium-ion battery system, test its chemical property, comprise cyclic voltammetric (CV), alternating-current impedance (EIS), constant current charge-discharge (GCD), leakage current, cycle life etc.
In order to verify the validity of above technical scheme, the present invention has carried out following test analysis checking, take embodiment 5 as example.
1, the specific conductivity variation with temperature curve of 1-butyl-3-Methylimidazole thiocyanate ion liquid
Fig. 1 is the specific conductivity variation with temperature curve that reacts the ionic liquid BmimSCN generating after raw material synthetic intermediate with Sodium Thiocyanate 99 for adopting N-Methylimidazole and bromination of n-butane.As can be seen from Figure, during room temperature, the specific conductivity of pure BmimSCN ionic liquid is in 4.0mS/cm left and right, this specific conductivity than common ionic liquid is significantly improved, mainly because negatively charged ion SCN-volume in BmimSCN ionic liquid is relatively little, ion migration speed is fast, and specific conductivity is significantly improved.But the specific conductivity of pure PmimSCN ionic liquid during than room temperature (4.7mS/cm left and right) is low, is mainly due to the alkyl chain length in BmimSCN positively charged ion, and it is large that ion volume becomes, and rate travel slows down, and specific conductivity is low.By figure, be it can also be seen that, the specific conductivity of BmimSCN ionic liquid becomes along with the rising of temperature greatly, meets the universal law of ionic liquid electrolyte.
2, the cyclic voltammetry curve of 1-butyl-3-Methylimidazole thiocyanate ion liquid
In order to investigate the chemical property of sample, measured the cyclic voltammetry curve of sample in Graphene ultracapacitor.As can be seen from the figure, in CV curve, without obvious redox peak, charge and discharge process symmetry is good, shows electric double layer capacitance characteristic, and electrochemical window is 2.5V.As can be seen from Figure, in scanning speed, be 5mV/s, during 10mV/s, the shape of CV curve is close to rectangle, illustrate and there is good electric double layer capacitance characteristic, but along with the increase of scanning speed, it is larger that the shape of CV curve departs from rectangle, this is because under less scanning speed, ion mobility is slower, in electrode materials, effectively the utilization ratio of active substance is higher, makes to discharge and recharge more thorough, and therefore the capacitance characteristic of performance is good.Increase along with scanning speed, on electrode, current density raises, electrolyte ion concentration moment decline on electrode/electrolyte interface, make the ion rate of diffusion in electrolytic solution slack-off, the electrolyte ion number on surface can not reach the needed number of ions of electrode charge fast, causes on electrode and causes departing from larger by the caused polarization of Liquid Phase Diffusion.
The present invention does not limit to above-mentioned cited embodiment, those skilled in the art can be according to the present invention principle of work and the embodiment that provides above, can make the various modifications that are equal to, the replacement being equal to, parts increase and decrease and reconfigure, thereby forming how new embodiment.
Claims (8)
1. a preparation method for thiocyanate ion functionalized ion liquid electrolytic solution, is characterized in that, comprising:
Step 1: under nitrogen environment protection, get amine or Phosphorus monomer joins in flask, in flask, drip haloalkyl hydrocarbon, dropwise and rear mixture in flask is heated, 4-10h again refluxes after being warming up to 60-110 ℃, after finishing, reaction is cooled to room temperature, with organic solvent washing, remove unreacted material 3 times again, rotary evaporation is removed organic solvent, product obtained above is heated to be decompressed to 0.1MPa vacuum-drying 8-12h at 60-80 ℃, obtains halogenation ionic liquid intermediate;
Step 2: halogenation ionic liquid intermediate and the Sodium Thiocyanate 99 (NaSCN) of getting above-mentioned preparation, ratio according to mol ratio 1:1-1:5 is mixed, after mixing, adding molar weight is in Sodium Thiocyanate 99 2-10 acetone solvent doubly, magnetic agitation 12-72h at room temperature, reaction finishes rear standing, remove by filter throw out, filtrate rotary evaporation is removed to acetone solvent, to adding molar weight in filtrate, be Sodium Thiocyanate 99 2-10 methylene dichloride organic solvent doubly again, magnetic agitation 1-5h at room temperature, reaction finishes rear standing, remove by filter the sodium salt in solution, filtrate rotary evaporation is removed to methylene dichloride organic solvent, finally mixing solutions obtained above is heated to be decompressed at 60-80 ℃ 0.1MPa vacuum-drying 8-12h, the final thiocyanate ion liquid that obtains.
2. the preparation method of a kind of thiocyanate ion functionalized ion liquid electrolytic solution according to claim 1, is characterized in that: add described amine in flask or the mol ratio 1:5 of Phosphorus monomer and haloalkyl hydrocarbon.
3. the preparation method of a kind of thiocyanate ion functionalized ion liquid electrolytic solution according to claim 1, is characterized in that: described amine or Phosphorus monomer comprise: N-Methylimidazole.
4. the preparation method of a kind of thiocyanate ion functionalized ion liquid electrolytic solution according to claim 1, is characterized in that: described haloalkyl hydrocarbon comprises: bromo hexane, n-propyl bromide or bromination of n-butane.
5. the preparation method of a kind of thiocyanate ion functionalized ion liquid electrolytic solution according to claim 1, is characterized in that: described organic solvent is the solvent that ratio that acetoneand ethyl acetate is 1:1-1:5 according to mol ratio is mixed.
6. the preparation method of a kind of thiocyanate ion functionalized ion liquid electrolytic solution according to claim 1, is characterized in that: described halogenation ionic liquid intermediate is comprised of X positively charged ion and Y negatively charged ion, and its general formula is: [X] Y, described Y negatively charged ion comprises: F
-, Cl
-, Br
-and I
-, described X positively charged ion comprises: alkyl imidazolium cation, pyroles positively charged ion, pyrrolidines positively charged ion, pyridines positively charged ion, piperidines positively charged ion, quaternary amines positively charged ion or quaternary phosphonium cationoid,
Described alkyl imidazolium cation, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 0-12 carbon atom, and R
2for containing the saturated or undersaturated alkyl of 1-25 carbon atom;
Described pyroles positively charged ion, structure is as follows: (having added one)
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom.
Described pyrrolidines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom.
Described pyridines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom;
Described piperidines positively charged ion, structure is as follows:
In formula, R is the saturated or undersaturated alkyl that contains 1-25 carbon atom, R
1for containing the saturated or undersaturated alkyl of 1-12 carbon atom;
Described quaternary amines positively charged ion, structure is as follows:
R in formula
1, R
2, R
3, R
4for containing the saturated or undersaturated alkyl of 1-25 carbon atom;
Described quaternary phosphonium cationoid, structure is as follows:
R in formula
1, R
2, R
3, R
4, R
5, R
6for containing the saturated or undersaturated alkyl of 1-25 carbon atom.
7. the preparation method of a kind of thiocyanate ion functionalized ion liquid electrolytic solution according to claim 1, is characterized in that: described halogenation ionic liquid intermediate comprises: 1-ethyl-3-methylimidazole bromine salt (EmimBr), 1-propyl group-3-Methylimidazole bromine salt (PmimBr) and 1-butyl-3-Methylimidazole bromine salt (BmimBr).
8. the preparation method of a kind of thiocyanate ion functionalized ion liquid electrolytic solution according to claim 1, it is characterized in that: described thiocyanate ion liquid is by thiocyanate ion negatively charged ion and cation composition, and described positively charged ion comprises: imidazoles, pyrroles, tetramethyleneimine, pyridine, piperidines, quaternary ammonium salt or quaternary alkylphosphonium salt.
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| CN107275120A (en) * | 2017-07-25 | 2017-10-20 | 陕西科技大学 | A kind of electrolysis additive and its application in lithium ion hydridization ultracapacitor |
| CN111239222A (en) * | 2020-01-16 | 2020-06-05 | 郑州大学 | Ionic liquid electrolyte and electrochemical gas sensor |
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| CN107275120A (en) * | 2017-07-25 | 2017-10-20 | 陕西科技大学 | A kind of electrolysis additive and its application in lithium ion hydridization ultracapacitor |
| CN111239222A (en) * | 2020-01-16 | 2020-06-05 | 郑州大学 | Ionic liquid electrolyte and electrochemical gas sensor |
| CN111239222B (en) * | 2020-01-16 | 2022-12-02 | 郑州大学 | Ionic liquid electrolyte and electrochemical gas sensor |
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