CN103390502B - Morpholine ionic liquid/gel polymer electrolyte membrane and preparation method thereof - Google Patents
Morpholine ionic liquid/gel polymer electrolyte membrane and preparation method thereof Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
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Abstract
A kind of Morpholine ionic liquid/gel polymer electrolyte membrane, comprises polyacrylonitrile substrate and miscible in the morpholinium ion liquid of polyacrylonitrile, and morpholinium ion liquid has a following structural formula:Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one；The mass ratio of polyacrylonitrile and morpholinium ion liquid is 100: 30 ~ 100: 50.It is high that this morpholinium ion liquid has electrical conductivity, and fusing point is low, the advantage that electrochemical window is wide, and this morpholinium ion liquid is non-volatile, non-combustible and Heat stability is good, and therefore, morpholinium ion liquid is applicable to prepare the electrolyte that safety is higher.Morpholinium ion liquid is miscible forms Morpholine ionic liquid/gel polymer electrolyte membrane in polyacrylonitrile, the advantage that this Morpholine ionic liquid/gel polymer electrolyte membrane has morpholinium ion liquid and gelatin polymer concurrently, this gel polymer electrolyte film being combined by ionic liquid no longer has the phenomenons such as solvent volatilization and leakage, and its safety is greatly improved.
Description
Technical field
The present invention relates to Morpholine ionic liquid/gel polymer electrolyte membrane and preparation method thereof.
Background technology
Ultracapacitor is a kind of novel energy storage component between rechargeable battery and capacitor, have volume little, hold
Amount is big, charging rate fast, have extended cycle life, discharging efficiency height, operating temperature range width, good reliability and contaminant-free maintenance-free etc.
Advantage, is a kind of novel, efficient, practical energy accumulating device, thus is widely used in military field, mobile communication dress
Put, computer and the AC-battery power source etc. of electric automobile.
Ultracapacitor working electrolyte is divided into aqueous electrolyte, organic liquid electrolyte and polymer dielectric.Water system
The decomposition voltage of electrolyte is low, thus studies less.The advantage of now widely used liquid electrolyte is that electrical conductivity is high, but
Owing to containing organic solvent inflammable, volatile, it discharges fuel gas in charge and discharge process, particularly at some very
Under rule working condition, (such as high-power discharge and recharge, super-charge super-discharge etc.) produce big calorimetric and can accelerate the generation of gas, in causing battery
Pressure increases, and gas leaks, blast the most on fire, thus there is serious potential safety hazard.Polymer dielectric ultracapacitor because of
There is the advantages such as safety, No leakage, leakage current be little and studied persons are paid attention to.Electrical conductivity under solid polymer electrolyte room temperature
Relatively low (10-5~10-4S/cm), use application to be restricted, thus gel polymer electrolyte becomes research emphasis.
Ionic liquid has electrical conductivity height, fusing point is low, electrochemical window width, non-volatile, non-combustible, Heat stability is good etc. are excellent
Gesture.In recent years, ionic liquid/gel polymer electrolyte increasingly enjoys the concern of people.
Summary of the invention
Based on this, it is necessary to for the problem that existing liquid electrolyte safety is the highest, it is provided that a kind of safety is higher
Morpholine ionic liquid/gel polymer electrolyte membrane and preparation method thereof.
A kind of Morpholine ionic liquid/gel polymer electrolyte membrane, comprises polyacrylonitrile substrate and miscible in described poly-third
The morpholinium ion liquid of alkene nitrile, described morpholinium ion liquid has a following structural formula:
Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one；Described polyacrylonitrile and morpholinium ion
The mass ratio of liquid is 100: 30 ~ 100: 50.
Wherein in an embodiment, the relative molecular weight of described polyacrylonitrile is 10 ~ 600,000.
The application in ultracapacitor or lithium ion battery of the above-mentioned Morpholine ionic liquid/gel polymer electrolyte membrane.
The preparation method of a kind of Morpholine ionic liquid/gel polymer electrolyte membrane, comprises the steps:
Step one: in mass ratio 100: 30 ~ 50: 20 ~ 40 polypropylene nitriles, morpholinium ion liquid and organic solvent, adds
Heat makes polyacrylonitrile dissolve to 40 ~ 60 DEG C and stirring, is formed as homogeneous mixed liquor, and described morpholinium ion liquid has following structure
Formula:
Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one；
Step 2: cast on substrate by described homogeneous mixed liquor, then by the described substrate being cast with homogeneous mixed liquor
It is vacuum dried 24 ~ 28 hours at 80 ~ 100 DEG C, peels off the film on described substrate after being cooled to room temperature and obtain described morpholinium ion
Liquid/gel polymer dielectric film.
Wherein in an embodiment, the relative molecular weight of described polyacrylonitrile is 10 ~ 600,000.
Wherein in an embodiment, described organic solvent is dimethylformamide, N-Methyl pyrrolidone or ethylene
Alkene ester.
Wherein in an embodiment, described morpholinium ion liquid is prepared as follows:
By the one in methoxy ethoxy ethyl chloride, methoxy ethoxy bromoethane and methoxy ethoxy iodoethane with
After N-methylmorpholine 1.05: 1 ~ 1.2: 1 mixing in molar ratio, microwave radiation heats 20 ~ 40 seconds, then stirs 10 ~ 15 seconds, repeats
Described heating and whipping step obtain halogenation N-methoxyethoxyethyl-N-methylmorpholine, described halogenation N-methoxyl group for 3 ~ 6 times
Ethoxyethyl group-N-methylmorpholine is chlorination N-methoxyethoxyethyl-N-methylmorpholine, bromination N-methoxy ethoxy second
Base-N-methylmorpholine or iodate N-methoxyethoxyethyl-N-methylmorpholine；
It is M by described halogenation N-methoxyethoxyethyl-N-methylmorpholine and formula+Y-Salt in molar ratio 1: 1 ~ 1:
Adding in deionized water after 1.1 mixing, there is ion-exchange reactions in stirring, isolated and purified after obtain that there is following structural formula
Quinoline ionic liquid:
Wherein, M+Selected from Na+、K+And NH4 +In one；Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one
Kind.
Wherein in an embodiment, described methoxy ethoxy ethyl chloride, methoxy ethoxy bromoethane and methoxyl group
The mixture of a kind of and N-methylmorpholine in ethyoxyl iodoethane is to heat under microwave irradiation power 200 ~ 300W, weight
Wash by ethyl acetate after obtaining reactant cooling after multiple described heating and whipping step 3 ~ 6 times, the product then washing obtained
Thing vacuum drying obtains the halogenation N-methoxyethoxyethyl-N-methylmorpholine purified.
Wherein in an embodiment, the temperature of described ion-exchange reactions is 15 ~ 30 DEG C, and the time is 8 ~ 24 hours.
Wherein in an embodiment, described purification procedures is as follows: by halogenation N-methoxyethoxyethyl-N-first
Base morpholine with there is formula M+Y-Salt stirring reaction after obtain mixed liquor dichloromethane extraction, then anti-with deionized water
Extraction is until obtained aqueous phase is with saturated AgNO3Aqueous solution is titrated to produce without precipitation, is evaporated by dichloromethane extract dense
Contracting final vacuum is dried to obtain described morpholinium ion liquid.
Above-mentioned Morpholine ionic liquid/gel polymer electrolyte membrane comprises polyacrylonitrile substrate and miscible in polyacrylonitrile
Morpholinium ion liquid, morpholinium ion liquid has that electrical conductivity is high, and fusing point is low, the advantage that electrochemical window is wide, and its electrical conductivity is 2 ~
6ms/cm, fusing point about-30 DEG C, electrochemical window at about 5.0V, and this morpholinium ion liquid is non-volatile, non-combustible and
Heat stability is good, decomposition temperature is higher than 320 DEG C.Therefore, above-mentioned morpholinium ion liquid is applicable to prepare the electrolysis that safety is higher
Matter.This morpholinium ion liquid miscible in polyacrylonitrile formed Morpholine ionic liquid/gel polymer electrolyte membrane, this morpholine from
Sub-liquid/gel polymer dielectric film has the advantage of morpholinium ion liquid and gelatin polymer concurrently, this multiple by ionic liquid
The gel polymer electrolyte film closed no longer has solvent volatilization and the phenomenon such as leakage, relative to inflammable, volatile, there is blast peace
For the organic liquid electrolyte of full hidden danger, its safety is greatly improved.
Accompanying drawing explanation
Fig. 1 is the preparation method flow chart of the morpholinium ion liquid of an embodiment；
Fig. 2 is the preparation method flow chart of the Morpholine ionic liquid/gel polymer electrolyte membrane of an embodiment.
Detailed description of the invention
Below by way of the drawings and the specific embodiments to above-mentioned Morpholine ionic liquid/gel polymer electrolyte membrane and system thereof
Preparation Method is expanded on further.
A kind of morpholinium ion liquid, has a following structural formula:
Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one.
It is high that this morpholinium ion liquid has electrical conductivity, and the advantage that fusing point is low and electrochemical window is wide, its electrical conductivity is 2-
6ms/cm, fusing point about-30 DEG C, electrochemical window at about 5.0V, and this morpholinium ion liquid is non-volatile, non-combustible and
Heat stability is good, decomposition temperature is higher than 320 DEG C.Therefore, this morpholinium ion liquid is suitable for preparing safety and is preferably electrolysed
Matter.
Refer to Fig. 1, the preparation method of the morpholinium ion liquid of an embodiment, comprise the steps:
Step S110: by methoxy ethoxy ethyl chloride, methoxy ethoxy bromoethane and methoxy ethoxy iodoethane
In one and N-methylmorpholine in molar ratio 1.05: 1 ~ 1.2: 1 mix after microwave radiation heat 20 ~ 40 seconds, then stir 10 ~
15 seconds, Repeat-heating and whipping step obtained halogenation N-methoxyethoxyethyl-N-methylmorpholine, this halogenation N-first for 3 ~ 6 times
Epoxide ethoxyethyl group-N-methylmorpholine is chlorination N-methoxyethoxyethyl-N-methylmorpholine, bromination N-methoxyl group ethoxy
Base ethyl-N-methylmorpholinium or iodate N-methoxyethoxyethyl-N-methylmorpholine.
One in methoxy ethoxy ethyl chloride, methoxy ethoxy bromoethane and methoxy ethoxy iodoethane and N-
The mixture of methyl morpholine heats under microwave irradiation power 200 ~ 300W.Compared with traditional heating, microwave heating can be big
Big organic synthesis speed of accelerating, in the shortening response time, improves production efficiency.After heating 20 ~ 40 seconds, stir 10 ~ 15 seconds, weight
After being added with heat and whipping step 3 ~ 6 times, stir to room temperature, wash three times by ethyl acetate.It is vacuum dried at 80 DEG C, obtains halogen
Change N-methoxyethoxyethyl-N-methylmorpholine.Halogenation N-methoxyethoxyethyl-N-methylmorpholine is light yellow solid
Body.
Step S120: halogenation N-methoxyethoxyethyl-N-methylmorpholine step 110 prepared and formula are M+Y-
Salt 1: 1 ~ 1: 1.1 mixing in molar ratio after add in deionized water, stirring reaction, isolated and purified after obtain that there is following structure
The morpholinium ion liquid of formula:
Wherein, M+Selected from Na+、K+And NH4 +In one；Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one
Kind.
Halogenation N-methoxyethoxyethyl-N-methylmorpholine and formula are M+Y-Salt in deionized water in 15 ~ 30 DEG C
There is ion-exchange reactions in lower stirring, obtains mixed liquor after reacting 8 ~ 24 hours, is extracted 3 times by this mixed liquor dichloromethane,
Combining extraction liquid, the most every time with deionized water back extraction until with saturated AgNO3Aqueous solution titration aqueous phase is produced as without precipitation
Only, after being concentrated with Rotary Evaporators by dichloromethane, at 80 DEG C, vacuum drying obtains colourless liquid in 48 hours, i.e. has
The morpholinium ion liquid of following structural formula:
Wherein, M+Selected from Na+、K+And NH4 +In one；Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one
Kind.
It is appreciated that the response time is not limited to 8 ~ 24 hours, as long as making halogenation N-methoxyethoxyethyl-N-methyl
Morpholine and formula are M+Y-Reactant salt completely.
Step S120, using deionized water as reaction dissolvent, reduces the use of organic solvent, environmentally friendly, and cost
Low.
The net reaction of preparing of morpholinium ion liquid is:
Wherein,For
M+Selected from Na+、K+And NH4 +In one；Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one.
The preparation method preparation technology of this morpholinium ion liquid is simple, and reaction condition is gentle, and the response time is short, reaction efficiency
Height, cost is relatively low, it is easy to prepare on a large scale.
The raw material of preparing of this morpholinium ion liquid is N-methylmorpholine and methoxy ethoxy halothane, prepares raw material and takes
Must be relatively easy to, price is relatively inexpensive, it is easy to popularization and application.
The Morpholine ionic liquid/gel polymer electrolyte membrane of one embodiment, comprise polyacrylonitrile substrate and miscible in
The morpholinium ion liquid of polyacrylonitrile, this morpholinium ion liquid has a following structural formula:
Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one；Polyacrylonitrile and morpholinium ion liquid
Mass ratio be 100: 30 ~ 100: 50.
It is preferable that polyacrylonitrile has film property, and film-strength is high, and electrochemical stability window width does not decomposes in organic electrolyte
Advantage, be the gel polymer electrolyte skeletal support material of function admirable.
In present embodiment, the relative molecular weight of polyacrylonitrile is 10 ~ 600,000.For reaching ultracapacitor or lithium battery etc.
Application requirement, dielectric film must have preferable mechanical performance and electrode tack.Polyacrylonitrile is as ionic liquid/solidifying
The skeletal support carrier of xanthan polymer electrolyte should have preferable mechanical performance and electrode tack to meet dielectric film
Requirement.Molecular weight has preferable intensity and the viscosity being suitable at the polyacrylonitrile of 10 ~ 600,000, makes gel based on polyacrylonitrile
Polymer dielectric has preferable mechanical performance and electrode tack.
Room temperature morpholinium ion liquid is incorporated in the polyacrylonitrile of satisfactory mechanical property formation morpholinium ion liquid/gel
Polymer dielectric, makes the advantage that this gel polymer electrolyte has morpholinium ion liquid and gel polymer electrolyte concurrently.This
Plant the gel polymer electrolyte film being combined by ionic liquid and no longer have the phenomenons such as solvent volatilization and leakage, relative to inflammable, easy
Volatilizing, exist for the organic liquid electrolyte of explosion safety hidden danger, its safety is greatly improved, so that this morpholinium ion
The ultracapacitor of liquid/gel polymer dielectric film and the safety of lithium battery are improved.
Morpholinium ion liquid dispersion is in polyacrylonitrile, and both form stable membrane structure, good mechanical property, it is simple to super
Other electrochemical devices such as level capacitor assemble.This Morpholine ionic liquid/gel polymer electrolyte membrane can be processed into arbitrarily
Shape, it is adaptable to difform electrochemical device, and be conducive to preparing various ultra-thin electromechanical device.
Further, it is provided that above-mentioned Morpholine ionic liquid/gel polymer electrolyte membrane is at ultracapacitor or lithium ion
Application in battery.
Refer to Fig. 2, the preparation method of the Morpholine ionic liquid/gel polymer electrolyte membrane of an embodiment, including
Following steps:
Step S220: in mass ratio 100: 30 ~ 50: 20 ~ 40 polypropylene nitriles, morpholinium ion liquid and organic solvent,
Heating and stirring makes polyacrylonitrile dissolve, and makes polyacrylonitrile, morpholinium ion liquid and organic solvent be mixed into homogeneous mixed liquor,
This morpholinium ion liquid has a following structural formula:
Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one.
This morpholinium ion liquid is prepared by the preparation method of above-mentioned morpholinium ion liquid.The preparation of above-mentioned morpholinium ion liquid
Method cost is relatively low, can reduce the cost of Morpholine ionic liquid/gel polymer electrolyte membrane.
The molecular weight of this polyacrylonitrile is 10 ~ 600,000.Heated and stirred makes polyacrylonitrile dissolve, and the temperature of heating is 40 ~ 60
℃.At 40 ~ 60 DEG C, the modest viscosity of polyacrylonitrile, follow-up casting film.
Organic solvent is dimethylformamide (DMF), N-Methyl pyrrolidone (NMP) or ethylene carbonate (EC).Organic
The effect of solvent is to dissolve polyacrylonitrile and morpholinium ion liquid, and pore-creating on polyacrylonitrile, has solvent and plasticizer concurrently
Function.By miscible to organic solvent, polyacrylonitrile and morpholinium ion liquid, after film forming by organic solvent remove, stay micropore in order to
Absorption morpholinium ion liquid.Dimethylformamide (DMF), N-Methyl pyrrolidone (NMP) or ethylene carbonate (EC) and poly-third
The compatibility of alkene nitrile is good, and plasticizing efficiency is high.
The content of organic solvent is the highest, and the micropore that polyacrylonitrile is formed is the most, and the morpholinium ion liquid that can adsorb is more
Many, then can be effectively improved the electrical conductivity of Morpholine ionic liquid/gel polymer electrolyte membrane.But the micropore on polyacrylonitrile
The most, then the mechanical performance of polyacrylonitrile is the lowest.The mass ratio of polyacrylonitrile, morpholinium ion liquid and organic solvent is 100: 30
When ~ 50: 20 ~ 40, it is possible to obtain relatively mild mechanical performance and electrical conductivity.
Step S220 is carried out in dry inert gas shielding atmosphere, and noble gas can be nitrogen, argon or helium
Deng.
Step S240: cast on substrate by the homogeneous mixed liquor of step S220, then will be cast with homogeneous mixed liquor
Substrate is vacuum dried 24 ~ 28 hours, separates the film on substrate and obtain morpholinium ion liquid/gel polymer after being cooled to room temperature
Dielectric film.
Substrate is clean sheet glass or Teflon mould.Vacuum drying temperature is 80 ~ 100 DEG C.It is cast with all
After the substrate of phase mixed liquor is vacuum dried 24 ~ 28 hours, substrate forms transparent elastica.Glove at full noble gas
Case separates from substrate this elastica, i.e. obtains ionic liquid/gel polymer electrolyte film.
Glove box provides anaerobic, anhydrous and dustless environment, it is to avoid steam and dust are to morpholine ionic liquid/gel polymerisation
Thing dielectric film produces impact.
The preparation method technique of this Morpholine ionic liquid/gel polymer electrolyte membrane is simple, and cost of manufacture is low, is suitable for big
Prepared by technical scale, be conducive to developing ultra-thin, the various abnormity electrochemical devices such as ultracapacitor, lithium battery of overlarge area.
It it is below specific embodiment.
Embodiment 1
Preparing morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate, course of reaction is as follows
Shown in:
N-methylmorpholine (101g, 1mol) and methoxy ethoxy ethyl chloride (145.5g, 1.05mol) are mixed, stirring
Uniformly, under microwave irradiation power 240W, after heating 30 seconds, stir 15 seconds after taking-up, be so repeated 3 times, stir to room temperature, use
Ethyl acetate is washed three times.Be vacuum dried at 80 DEG C, obtain lurid solid, i.e. chlorination N-methoxyethoxyethyl-
N-methylmorpholine, productivity is 82%；
By this chlorination N-methoxyethoxyethyl-N-methylmorpholine (119.9g, 0.5mol) and NaBF4(60.5g,
0.55mol) being dissolved in 100mL deionized water, at 15 DEG C, stirring obtains mixed liquor in 8 hours, by this mixed liquor 250mL dichloro
Methane extracts 3 times, combining extraction liquid, the most every time with 60mL deionized water back extraction until with saturated AgNO3Aqueous solution titrates
Till aqueous phase produces without precipitation, after being concentrated with Rotary Evaporators by dichloromethane, 80 DEG C of vacuum drying obtain colourless in 48 hours
Liquid i.e. N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate；
The nuclear magnetic spectrum of prepared morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate
As follows: 1H NMR (CDCl3,400MHz, ppm): 3.84 (m, 2H), 3.73 (m, 2H), 3.62 (m, 2H), 3.57 (m, 2H),
3.38(m,2H),3.24(s,3H),2.95(s,3H),2.78(m,2H),2.65(m,2H),2.56(m,2H).
Prepare morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine tetrafluoroborate/gelatin polymer electricity
Solution plasma membrane:
Polyacrylonitrile, 50g N-methoxy that 100g relative molecular weight is 500,000 it is sequentially added in the there-necked flask of 500mL
Base oxethyl ethyl-N-methyl tetrafluoroborate and 20g dimethylformamide.Under the protection of dry nitrogen, heat up
To 40 DEG C, and stirring allows polyacrylonitrile dissolve, and makes system become homogeneous.By the solution-cast of above-mentioned mix homogeneously at clean glass
On glass sheet, it is transferred quickly in vacuum drying oven, is dried 24 hours at 100 DEG C, sloughs organic solvent.After being cooled to room temperature,
In the glove box of full nitrogen, separate elastica transparent on sheet glass be sub-morpholinium ion liquid N-methoxyl group ethoxy
Base ethyl-N-methylmorpholinium tetrafluoroborate/gel polymer electrolyte film.
Embodiment 2
Preparing morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate, course of reaction is as follows
Shown in:
N-methylmorpholine (101g, 1mol) and methoxy ethoxy bromoethane (201.3g, 1.1mol) being mixed, stirring is all
Even, under microwave irradiation power 200W, after heating 40 seconds, to take out stirring 10 seconds, be so repeated 4 times, stirring, to room temperature, uses acetic acid
Ethyl ester washs three times.It is vacuum dried at 80 DEG C, obtains lurid solid, i.e. bromination N-methoxyethoxyethyl-N-first
Base morpholine, productivity is 85%；
By this bromination N-methoxyethoxyethyl-N-methylmorpholine (142.1g, 0.5mol) and (96.6g, 0.53mol)
KPF6Being dissolved in 120mL deionized water, at 25 DEG C, stirring obtains mixed liquor in 16 hours, by this mixed liquor 250mL dichloromethane
Extract 4 times, combining extraction liquid, the most every time with 60mL deionized water back extraction until with saturated AgNO3Aqueous solution titration aqueous phase
Till producing without precipitation, after being concentrated with Rotary Evaporators by dichloromethane, 80 DEG C of vacuum drying obtain colourless liquid in 48 hours
Body i.e. N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate；
The nuclear magnetic spectrum of prepared morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate
As follows:
1H NMR(CDCl3,400MHz,ppm):3.85(m,2H),3.74(m,2H),3.64(m,2H),3.59(m,2H),
3.40(m,2H),3.24(s,3H),2.96(s,3H),2.78(m,2H),2.67(m,2H),2.58(m,2H).
Prepare morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine hexafluorophosphate/gelatin polymer electricity
Solution plasma membrane:
Polyacrylonitrile, 45g N-methoxy that 100g relative molecular weight is 100,000 it is sequentially added in the there-necked flask of 500mL
Base oxethyl ethyl-N-methyl limidazolium hexafluorophosphate and 30g N-Methyl pyrrolidone.Under the protection of dry argon, rise
Temperature is to 60 DEG C, and stirring allows polyacrylonitrile dissolve, and makes system become homogeneous.By the solution-cast of above-mentioned mix homogeneously in cleaning
On sheet glass, it is transferred quickly in vacuum drying oven, is dried 48 hours at 80 DEG C, sloughs organic solvent.After being cooled to room temperature,
In the glove box of full argon, separate elastica transparent on sheet glass be morpholinium ion liquid N-methoxy ethoxy
Ethyl-N-methylmorpholinium hexafluorophosphate/gel polymer electrolyte film.
Embodiment 3
Prepare double (fluoroform sulphonyl) inferior amine salt of morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine, instead
Answer process as follows:
N-methylmorpholine (101g, 1mol) and methoxy ethoxy iodoethane (276g, 1.2mol) being mixed, stirring is all
Even, under microwave irradiation power 300W, after heating 20 seconds, to take out stirring 10 seconds, be so repeated 6 times, stirring, to room temperature, uses acetic acid
Ethyl ester washs three times.It is vacuum dried at 80 DEG C, obtains lurid solid, i.e. iodate N-methoxyethoxyethyl-N-first
Base morpholine), productivity is 84%；
By this iodate N-methoxyethoxyethyl-N-methylmorpholine (165.6g, 0.5mol) and (159.5g, 0.5mol)
Double (fluoroform sulphonyl) imines potassium is dissolved in 150mL deionized water, and at 30 DEG C, stirring obtains mixed liquor in 24 hours, by this mixed liquor
Extract 6 times with 250mL dichloromethane, combining extraction liquid, the most every time with 60mL deionized water back extraction until with saturated AgNO3
Till aqueous solution titration aqueous phase produces without precipitation, after being concentrated with Rotary Evaporators by dichloromethane, 80 DEG C of vacuum drying 48 are little
Time obtain colourless liquid, i.e. double (fluoroform sulphonyl) inferior amine salt of N-methoxyethoxyethyl-N-methylmorpholine；
Double (fluoroform sulphonyl) inferior amine salt of prepared morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine
Nuclear magnetic spectrum as follows:
1H NMR(CDCl3,400MHz,ppm):3.86(m,2H),3.75(m,2H),3.64(m,2H),3.59(m,2H),
3.42(m,2H),3.26(s,3H),2.97(s,3H),2.78(m,2H),2.67(m,2H),2.59(m,2H).
Prepare double (fluoroform sulphonyl) inferior amine salt of morpholinium ion liquid N-methoxyethoxyethyl-N-methylmorpholine/solidifying
Xanthan polymer electrolytic salt film:
Polyacrylonitrile, 30gN-methoxyl group that 100g relative molecular weight is 600,000 it is sequentially added in the there-necked flask of 500mL
Double (fluoroform sulphonyl) inferior amine salt of ethoxyethyl group-N-Methylimidazole. and 20g ethylene carbonate.Protection at dry helium
Under, it is warmed up to 50 DEG C, and stirring allows polyacrylonitrile dissolve, and makes system become homogeneous.The solution-cast of above-mentioned mix homogeneously is existed
On clean sheet glass, it is transferred quickly in vacuum drying oven, is dried 36 hours at 90 DEG C, sloughs organic solvent.It is cooled to
After room temperature, the glove box of full helium separates elastica transparent on sheet glass and is morpholinium ion liquid N-methoxyl group
Double (fluoroform sulphonyl) inferior amine salt/gel polymer electrolyte film of ethoxyethyl group-N-methylmorpholine.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a morpholinium ion liquid/gel composites polymer electrolytes film, it is characterised in that comprise polyacrylonitrile substrate and mix
Being dissolved in the morpholinium ion liquid of described polyacrylonitrile, described morpholinium ion liquid has a following structural formula:
Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one；Described polyacrylonitrile and morpholinium ion liquid
Mass ratio be 100:30～100:50.
Morpholinium ion liquid/gel composites polymer electrolytes film the most according to claim 1, it is characterised in that described
The relative molecular weight of polyacrylonitrile is 10～600,000.
3. the morpholinium ion liquid/gel composites polymer electrolytes film as described in any one of claim 1 or 2 is at super capacitor
Application in device or lithium ion battery.
4. the preparation method of a morpholinium ion liquid/gel composites polymer electrolytes film, it is characterised in that include walking as follows
Rapid:
Step one: 100:30～50:20 in mass ratio～40 polypropylene nitriles, morpholinium ion liquid and organic solvent, heating
To 40～60 DEG C and stir and be formed as homogeneous mixed liquor, described morpholinium ion liquid has a following structural formula:
Wherein, Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one；
Step 2: cast on substrate by described homogeneous mixed liquor, then by the described substrate of homogeneous mixed liquor that is cast with 80
～be vacuum dried 24～28 hours at 100 DEG C, peel off the film on described substrate after being cooled to room temperature and obtain described morpholinium ion liquid
Body and gel polymer electrolyte film.
The preparation method of morpholinium ion liquid/gel composites polymer electrolytes film the most according to claim 4, its feature
Being, the relative molecular weight of described polyacrylonitrile is 10～600,000.
The preparation method of morpholinium ion liquid/gel composites polymer electrolytes film the most according to claim 4, its feature
Being, described organic solvent is dimethylformamide, N-Methyl pyrrolidone or ethylene carbonate.
The preparation method of morpholinium ion liquid/gel composites polymer electrolytes film the most according to claim 4, its feature
Being, described morpholinium ion liquid is prepared as follows:
By the one in methoxy ethoxy ethyl chloride, methoxy ethoxy bromoethane and methoxy ethoxy iodoethane and N-first
After base morpholine 1.05:1～1.2:1 in molar ratio mixing, microwave radiation heats 20～40 seconds, and institute is repeated in then stirring 10～15 seconds
State heating and whipping step 3～obtain halogenation N-methoxyethoxyethyl-N-methylmorpholine for 6 times, described halogenation N-methoxyl group
Ethoxyethyl group-N-methylmorpholine is chlorination N-methoxyethoxyethyl-N-methylmorpholine, bromination N-methoxy ethoxy second
Base-N-methylmorpholine or iodate N-methoxyethoxyethyl-N-methylmorpholine；
It is M by described halogenation N-methoxyethoxyethyl-N-methylmorpholine and formula+Y-Salt 1:1～1:1.1 in molar ratio
Adding in deionized water after mixing, there is ion-exchange reactions in stirring, isolated and purified after obtain the morpholine with following structural formula
Ionic liquid:
Wherein, M+Selected from Na+、K+And NH4 +In one；Y-Selected from BF4 -、PF6 -、(CF3SO2)2N-And CF3SO3 -In one.
The preparation method of morpholinium ion liquid/gel composites polymer electrolytes film the most according to claim 7, its feature
Be, the one in described methoxy ethoxy ethyl chloride, methoxy ethoxy bromoethane and methoxy ethoxy iodoethane with
The mixture of N-methylmorpholine is to heat under microwave irradiation power 200～300W, repeats described heating and whipping step 3
～wash by ethyl acetate after obtaining reactant cooling after 6 times, then the product vacuum that washing obtains is dried to obtain purification
Halogenation N-methoxyethoxyethyl-N-methylmorpholine.
The preparation method of morpholinium ion liquid/gel composites polymer electrolytes film the most according to claim 7, its feature
Being, the temperature of described ion-exchange reactions is 15～30 DEG C, and the time is 8～24 hours.
The preparation method of morpholinium ion liquid/gel composites polymer electrolytes film the most according to claim 7, it is special
Levying and be, described purification procedures is as follows: by halogenation N-methoxyethoxyethyl-N-methylmorpholine with there is formula M+Y-
Salt stirring reaction after the mixed liquor dichloromethane extraction that obtains, then with deionized water back extraction until obtained aqueous phase is used
Saturated AgNO3Aqueous solution is titrated to produce without precipitation, is dried to obtain by dichloromethane extract evaporation and concentration final vacuum described
Morpholinium ion liquid.
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| JP2002063813A (en) * | 2000-08-22 | 2002-02-28 | Daiso Co Ltd | Gel-form electrolyte made of ether compound, and electrochemical element using the same |
| CN1986534A (en) * | 2006-12-13 | 2007-06-27 | 武汉大学 | Compound containing morpholine cation radical and its synthesis process and use |
| CN101085762A (en) * | 2007-07-05 | 2007-12-12 | 上海交通大学 | Ionic liquid containing N-cyanoalkyl-N-alkylmorphinone cation and preparation method thereof |
| CN102993120A (en) * | 2011-09-19 | 2013-03-27 | 海洋王照明科技股份有限公司 | Morpholine-containing ionic liquid and preparation method thereof as well as electrolyte and application thereof |
| CN103387742A (en) * | 2012-05-08 | 2013-11-13 | 海洋王照明科技股份有限公司 | Imidazole ionic liquid/gel polymer electrolyte membrane and preparation method thereof |
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| JP2002063813A (en) * | 2000-08-22 | 2002-02-28 | Daiso Co Ltd | Gel-form electrolyte made of ether compound, and electrochemical element using the same |
| CN1986534A (en) * | 2006-12-13 | 2007-06-27 | 武汉大学 | Compound containing morpholine cation radical and its synthesis process and use |
| CN101085762A (en) * | 2007-07-05 | 2007-12-12 | 上海交通大学 | Ionic liquid containing N-cyanoalkyl-N-alkylmorphinone cation and preparation method thereof |
| CN102993120A (en) * | 2011-09-19 | 2013-03-27 | 海洋王照明科技股份有限公司 | Morpholine-containing ionic liquid and preparation method thereof as well as electrolyte and application thereof |
| CN103387742A (en) * | 2012-05-08 | 2013-11-13 | 海洋王照明科技股份有限公司 | Imidazole ionic liquid/gel polymer electrolyte membrane and preparation method thereof |
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