CN104558390B - Gel polymer electrolyte polymer and preparation method thereof and gel polymer electrolyte and preparation method thereof - Google Patents
Gel polymer electrolyte polymer and preparation method thereof and gel polymer electrolyte and preparation method thereof Download PDFInfo
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Abstract
A kind of gel polymer electrolyte polymer, with following structural formula：Wherein, 8000≤n≤12000.Above-mentioned gel polymer electrolyte polymer can effectively improve the performance of gel polymer electrolyte.In addition, the preparation method of gel polymer electrolyte polymer is also provided, and gel polymer electrolyte and preparation method thereof.
Description
Technical field
Technical field of lithium ion of the present invention, more particularly to a kind of gel polymer electrolyte polymer and its preparation
Method, and use the gel polymer electrolyte of the polymer and preparation method thereof.
Background technology
Can be in the battery of discharge and recharge, lithium ion battery be as a kind of mechanism of new electrochemical power sources, with high-energy-density, high electricity
Pressure, small volume, it is lightweight, have extended cycle life, memoryless, advantages of environment protection, than it is other can the battery of discharge and recharge have wider
General application.In recent years, it is also mixed power electric car（HEV）, plug-in hybrid electric automobile（PHEV）, pure electricity
Electrical automobile（EV）One of and the preferable energy storage device of small intelligent power network.
Liquid lithium ionic cell due to containing to moisture-sensitive, the inflammable, organic electrolyte that easily sets off an explosion and apply it
Safety issue be under suspicion.But the electrical conductivity of solid lithium ion battery is relatively low, the level of practical application is reached far away, is made
About the further development of lithium ion battery industry.Gradually sent out on liquid lithium ionic cell and solid lithium ion battery transition state
A kind of new type lithium ion battery --- the gel polymer lithium ion battery that exhibition is got up.Gel polymer electrolyte（GPE）It is to make
Liguid organic solvent is converted into gel with polymeric matrix, battery can be effectively prevented from and produce inflatable leakage, on fire from explosion etc.
Accident so that polymer Li-ion battery not only has higher security than traditional liquid electrolyte lithium ion battery, and
And there is higher electrical conductivity than solid electrolyte lithium ion battery, and it be able to can both be ensured with flexible and changeable in shape
The abundant contact of inside battery, can greatly improve the flexibility of battery shape-designing again, strengthen aesthetic property.Therefore gel polymerisation
Thing electrolyte is deeply probed into by researcher all the time, in the higher electric car of security requirement, electric tool, army
The application in the field such as thing and spacecraft.
Although the ionic conductivity of gel polymer electrolyte film made from conventional method at room temperature reach 2.39 ×
10-3S.cm-1, but its interface stability is bad, at room temperature, it is impossible at the same meet ionic conductivity, it is steady with the interface of lithium metal
The performances such as qualitative and electrochemical window need, and these problems directly govern further applying for GPE.
The content of the invention
In consideration of it, be necessary to provide a kind of polymer of performance that can effectively improve gel polymer electrolyte and its
Preparation method, and use the gel polymer electrolyte of the polymer and preparation method thereof.
A kind of gel polymer electrolyte polymer, with following structural formula：
Wherein, 8000≤n≤12000.
A kind of preparation method of gel polymer electrolyte polymer, comprises the following steps：
Under conditions of the atmosphere of protective gas and stirring, the emulsifying agent of 1~3 parts by weight is added to 60~72 parts by weight
Deionized water in dissolve, be subsequently added into Butyl Acrylate Monomer, styrene monomer, methyl methacrylate monomer and acrylonitrile
Monomer, is warming up to 50~65 DEG C and stirs insulation reaction 0.3~0.5 hour, under conditions of 50~65 DEG C are incubated, and addition 0.1~
The initiator of 0.5 parts by weight, stirring insulation reaction 5~8 hours, obtains polymer emulsion, wherein, the butyl acrylate list
Body, styrene monomer, the total weight parts of methyl methacrylate monomer and acrylonitrile monemer are 25~38 parts；And
Demulsification will be stirred in polymer emulsion addition demulsification liquid, and through suction filtration, wash and dry, obtain gelatin polymer
Electrolyte polymer, the gel polymer electrolyte polymer has following structural formula：
Wherein, 8000≤n≤12000.
In one of the embodiments, the emulsifying agent is lauryl sodium sulfate, ammonium lauryl sulfate or dodecane
Base potassium sulfate；The initiator is sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate；The feed postition of the initiator is dropwise addition,
And the speed being added dropwise is 1~2 drop/sec.
In one of the embodiments, the Butyl Acrylate Monomer, styrene monomer, methyl methacrylate monomer and
The mass ratio of acrylonitrile monemer is 1~2:1~2:1~4:1~4.
In one of the embodiments, the demulsification liquid is the aqueous solution for the aluminum sulfate that mass percentage concentration is 2%~5%；
And the volume of the aqueous solution of the aluminum sulfate is 1~2 times of the volume of the polymer emulsion.
In one of the embodiments, the step of washing is：The filter residue that suction filtration is obtained uses 30~45 DEG C successively
Deionized water, the absolute ethyl alcohol under normal temperature and deionized water washing, obtain washed product；
The step of the drying is：The washed product is dried 2~3 hours at 40~50 DEG C, then 55~60
It is dried in vacuo 12~24 hours at DEG C.
A kind of gel polymer electrolyte, including the electrolysis on the gelatin polymer film of gel polymerisation film and absorption
Liquid, the material of the gelatin polymer film is the polymer with following structural formula：
Wherein, 8000≤n≤12000.
In one of the embodiments, the thickness of the gelatin polymer film is 70~100 microns；The electrolyte it is molten
Matter is LiPF6、LiBF4、LiN(SO2CF3)2Or LiN (SO2F)2；The solvent of the electrolyte can be dimethyl carbonate, carbonic acid
At least one of diethylester, propene carbonate, ethylene carbonate and acetonitrile.
A kind of method for preparing gel polymer electrolyte, comprises the following steps：
Gel polymer electrolyte polymer is prepared according to the method described above, and the gelatin polymer has such as with polymer
Lower structural formula：
Wherein, 8000≤n≤12000；
At 30~75 DEG C, by the gel polymer electrolyte of 2~12 parts by weight with polymer stirring and dissolving in 88
In the solvent of~98 parts by weight, viscous solution is obtained；
Supporter is provided, the viscous solution is coated on the supporter, gelatin polymer film is obtained after drying；And
Under anaerobic, the gelatin polymer film is soaked in electrolyte 30~60 minutes, obtains gel polymerisation
Thing electrolyte.
In one of the embodiments, the material of the supporter is polyolefin；The solvent is N, N- dimethyl formyls
Amine, acetone or tetrahydrofuran.
Due to containing Butyl Acrylate Monomer, styrene monomer, methyl in above-mentioned gel polymer electrolyte polymer
Methacrylate monomer and acrylonitrile monemer, Butyl Acrylate Monomer make it have excellent caking property, and styrene monomer makes it
With good mechanical strength, acrylonitrile monemer makes its wider electrochemical window, and contains in methyl methacrylate monomer
Carbonyl so that it has excellent imbibition ability so that the gel prepared using above-mentioned gel polymer electrolyte with polymer
The ionic conductivity of polymer dielectric is higher, good and electrochemical window is wide with lithium metal compatibility, therefore, uses above-mentioned gel
Polymer dielectric polymer can effectively improve the performance of gel polymer electrolyte.
Brief description of the drawings
Fig. 1 is the method for preparing gel polymer electrolyte flow chart of an embodiment；
Fig. 2 is the preparation method flow chart of the gel polymer electrolyte polymer of an embodiment；
Fig. 3 is the gel polymer electrolyte polymer and olefin(e) acid butyl ester, styrene, methyl methacrylate of embodiment 1
Ester and the fine infared spectrum of propylene；
Fig. 4 is the scanning electron microscope (SEM) photograph of the gelatin polymer film of embodiment 1（SEM）；
Fig. 5 is the gel polymer electrolyte AC impedance curve of embodiment 1；
Fig. 6 is the thermogravimetric curve of the gelatin polymer film of embodiment 1（TG）；
Fig. 7 is the electricity that the gel polymer electrolyte of embodiment 1 and lithium metal are assembled into the battery that structure is SS/GPE/Li
Chemically stable window test curve figure；
Fig. 8 be the gel polymer electrolyte of embodiment 1 and lithium metal to be assembled into structure be Li/GPE/Li button cells
Starting, the interface resistance figure after five days and after ten days；
Fig. 9 is that the structure of embodiment 1 is Li/GPE/LiNi0.5Mn1.5O42025 type button gel polymer lithium ions electricity
The cyclic curve figure of pond and traditional liquid lithium ionic cell at 0.5C multiplying powers, 55 DEG C.
Embodiment
Below mainly in combination with drawings and the specific embodiments to gel polymer electrolyte polymer and preparation method thereof and
Gel polymer electrolyte and preparation method thereof is described in further detail.
The gelatin polymer polymer of one embodiment, with following structural formula：
Wherein, 8000≤n≤12000.
Due to containing Butyl Acrylate Monomer, styrene monomer, methyl in above-mentioned gel polymer electrolyte polymer
Methacrylate monomer and acrylonitrile monemer, Butyl Acrylate Monomer make it have excellent caking property, and styrene monomer makes it
With good mechanical strength, acrylonitrile monemer makes its wider electrochemical window, and contains in methyl methacrylate monomer
Carbonyl so that it has excellent imbibition ability so that the gel prepared using above-mentioned gel polymer electrolyte with polymer
The ionic conductivity of polymer dielectric is higher, good and electrochemical window is wide with lithium metal compatibility, therefore, uses above-mentioned gel
Polymer dielectric polymer can effectively improve the performance of gel polymer electrolyte.
The gelatin polymer polymer dielectric of one embodiment, including gel polymerisation film and absorption are in gelatin polymer
Electrolyte on film, the material of gelatin polymer film is the polymer with following structural formula：
Wherein, 8000≤n≤12000.
Wherein, electrolyte can be electrolyte commonly used in the art.In the present embodiment, the solute of electrolyte can be
LiPF6、LiBF4、LiN(SO2CF3)2Or LiN (SO2F)2；The solvent of electrolyte can be dimethyl carbonate, diethyl carbonate, carbon
At least one of acid propylene ester, ethylene carbonate and acetonitrile.It is preferred that, the solute of electrolyte is LiPF6, solvent is carbonic acid two
The mixed liquor of methyl esters and ethylene carbonate, and the volume ratio of dimethyl carbonate and ethylene carbonate is 1:1, and the concentration of electrolyte
For 0.5~1mol/L.
Wherein, the thickness of gelatin polymer film is 70~100 microns, if the thickness of gelatin polymer film is too thick, can be caused
Film resistance increases, and then reduces the electrical conductivity of gel polymer electrolyte, if the thickness of gelatin polymer film is too thin, is attached to polyene
Amount of polymers on hydrocarbon is just less, and the performance to gel polymer electrolyte improves unobvious.
Above-mentioned gel polymer electrolyte includes the electrolyte of gel polymerisation film and absorption on gelatin polymer film, and should
The above-mentioned gel polymer electrolyte polymer of material of gelatin polymer film, due to containing butyl acrylate list in the polymer
Body, styrene monomer, methyl methacrylate monomer and acrylonitrile monemer, Butyl Acrylate Monomer make it have excellent bonding
Property, styrene monomer makes it have good mechanical strength, and acrylonitrile monemer makes its wider electrochemical window, and metering system
Contain carbonyl in sour methylmethacrylate monomer so that it has excellent imbibition ability so that the ion of above-mentioned gel polymer electrolyte
Conductance is higher, good and electrochemical window is wide with lithium metal compatibility, and therefore, above-mentioned gel polymer electrolyte has preferable
Performance.And above-mentioned gel polymer electrolyte is under the high temperature conditions, the lithium ion battery of above-mentioned gel polymer electrolyte is used
Still there is preferable cyclical stability.
As shown in figure 1, the method for preparing gel polymer electrolyte of an embodiment, comprises the following steps：
Step S100：Gel polymer electrolyte polymer is prepared, gel polymer electrolyte has such as with polymer
Lower structural formula：
Wherein, 8000≤n≤12000.
Wherein, also referring to Fig. 2, the preparation method of gel polymer electrolyte polymer comprises the following steps：
Step S110：Under conditions of the atmosphere of protective gas and stirring, the emulsifying agent of 1~3 parts by weight is added to 60
Dissolved in the deionized water of~72 parts by weight, be subsequently added into Butyl Acrylate Monomer, styrene monomer, methyl methacrylate list
Body and acrylonitrile monemer, are warming up to 50~65 DEG C of insulation reactions 0.3~0.5 hour, under conditions of 50~65 DEG C are incubated, and add
The initiator of 0.1~0.5 parts by weight, stirring insulation reaction 5~8 hours, obtains polymer emulsion, wherein, butyl acrylate list
Body, styrene monomer, the total weight parts of methyl methacrylate monomer and acrylonitrile monemer are 25~38 parts.
In the particular embodiment, butyl acrylate, styrene, methyl methacrylate and acrylonitrile monemer are added it
It is preceding also to include respectively being steamed Butyl Acrylate Monomer, styrene monomer, methyl methacrylate monomer and acrylonitrile monemer
Evaporate, to remove the hydroquinone of polymerization retarder in each monomer.
Wherein, the mass ratio of Butyl Acrylate Monomer, styrene monomer, methyl methacrylate monomer and acrylonitrile monemer
For 1~2:1~2:1~4:1~4.Because soft monomer has larger viscosity, when the amount for adding butyl acrylate soft monomer is larger
When, the polymer synthesized has been colloidal, it is impossible to continue next step experiment, and acrylonitrile is hard monomer, there is larger fragility,
Fragility can be reduced using the caking property of soft monomer, when the amount of hard monomer is larger, the polymer being attached on polyolefin easily falls,
So as to influence battery performance.
Wherein, the atmosphere of protective gas refers to the atmosphere of nitrogen, argon gas, helium or neon.
Wherein, in the present embodiment, emulsifying agent is added to the water, and adds Butyl Acrylate Monomer, styrene monomer, methyl
Methacrylate monomer and acrylonitrile monemer, and initiator is added, the rotating speed of stirring is 200~250 revs/min.This
The range of speeds can both make the various material mixings of addition uniform, can prevent material from being sputtered out in adition process again.
Wherein, add initiator and continue the rotating speed of stirring for 600~850 revs/min., can by rotating speed control in this scope
So that the material added is sufficiently stirred for, it is well mixed, because the organic phase and aqueous phase that add are mutual exclusive, prevents material mistake
It is poly-, so that reaction is more complete.
Wherein, emulsifying agent can be emulsifying agent commonly used in the art, preferably lauryl sodium sulfate, dodecyl sulphate
Ammonium or dodecyl sulphate potassium.
Wherein, initiator can be initiator commonly used in the art, preferably sodium peroxydisulfate, potassium peroxydisulfate or persulfuric acid
Ammonium.In the particular embodiment, the feed postition of initiator is is added dropwise, and the speed that the speed being added dropwise is is 1~2 drop/sec.If
The excessive velocities of dropwise addition, monomer is easy to occur to gather reaction, and in order to prevent from gathering reaction, control adds the speed of initiator
Degree, so as to reduce the contact area of initiator and material.
Step S120：Demulsification will be stirred in polymer emulsion addition demulsification liquid, and through suction filtration, wash and dry, obtain gel
Polymer dielectric polymer, the gel polymer electrolyte polymer has following structural formula：
Wherein, 8000≤n≤12000.
Wherein, demulsification liquid is the aluminum sulfate that mass percentage concentration is 2%~5%（Al2（SO4）3）The aqueous solution.And aluminum sulfate
The volume of the aqueous solution be 1~2 times of volume of polymer emulsion.If the volume for the liquid that is demulsified is very little, it is impossible to make polymer emulsion
Demulsification completely, if the volume of demulsification liquid is too many, can make troubles to operator.It is appreciated that demulsification liquid can also select to use it
His ionic surfactant demulsification liquid, for example, cetylpyridinium bromide.
Wherein, the step of washing is：The filter residue that suction filtration is obtained is successively using under 30~45 DEG C of deionized water, normal temperature
Absolute ethyl alcohol and deionized water washing, obtain washed product.In the particular embodiment, the filter residue that suction filtration is obtained is used first
30~45 DEG C of deionized water is cleaned 4~6 times, the washes of absolute alcohol 5~8 times under normal temperature is reused, then using under normal temperature
Deionized water clean 8~10 times.Dry step is：Washed product is dried 2~3 hours at 40~50 DEG C, Ran Hou
It is dried in vacuo 12~24 hours at 55~60 DEG C.In the particular embodiment, washed product is dried 2~3 at 40~50 DEG C
Hour is convection oven using equipment；It is vacuum drying chamber that the equipment used for 12~24 hours is dried at 55~60 DEG C.
Contain Butyl Acrylate Monomer, styrene list in gel polymer electrolyte polymer prepared by the above method
Body, methyl methacrylate monomer and acrylonitrile monemer, Butyl Acrylate Monomer make it have excellent caking property, styrene list
Body makes it have good mechanical strength, and acrylonitrile monemer makes its wider electrochemical window, and methyl methacrylate monomer
In contain carbonyl so that it has excellent imbibition ability so that using the above method prepare gel polymer electrolyte use
The ionic conductivity of gel polymer electrolyte prepared by polymer is higher, good and electrochemical window is wide with lithium metal compatibility,
Enable effectively improves the property of gel polymer electrolyte using above-mentioned gel polymer electrolyte polymer
Energy.
And the preparation method of above-mentioned gel polymer electrolyte polymer is simple to operate, and cost of material is cheap, source
Extensively.
Step S200：At 30~75 DEG C, by the gel polymer electrolyte of 2~12 parts by weight polymer stirring and dissolving
In the solvent of 88~98 parts by weight, viscous solution is obtained.
Wherein, solvent can be solvent commonly used in the art, preferably DMF（DMF）, acetone or four
Hydrogen furans（THF）.
Step S300：Supporter is provided, viscous solution is coated on supporter, gelatin polymer film is obtained after drying.
Wherein, the gelatin polymer film obtained after drying has very strong absorbency and liquid retention.Because the polymerization
Thing is selected is used as one of monomer, methyl methacrylate with absorbency and the stronger methyl methacrylate of liquid retention performance
Polar bond C=O in ester has fabulous compatibility with electrolyte, so as to improve the absorbent of polymer film.Specifically implementing
In example, it is coating machine that viscous solution is coated on to the equipment used on supporter.
Wherein, the drying steps in step S300 are：The supporter for being coated with viscous solution is dried in vacuo at room temperature
12~24 hours.
Wherein, the material of supporter can be support body material commonly used in the art, preferably polyolefin, and polyolefin is not only
Preparation is simple, abundant raw material, and price is also cheap, more preferably polyethylene film（PE）, polypropylene screen（PP）Or by polypropylene,
Polyethylene and the three-layer type composite membrane of polypropylene formation（PP-PE-PP）.
Step S400：Under anaerobic, gelatin polymer film is soaked in electrolyte 30~60 minutes, obtains gel
Polymer dielectric.
Wherein, oxygen free condition is referred under conditions of the inert gases such as nitrogen, helium, argon gas.
Wherein, electrolyte can be electrolyte commonly used in the art.In the present embodiment, the solute of electrolyte can be
LiPF6、LiBF4、LiN(SO2CF3)2Or LiN (SO2F)2；The solvent of electrolyte can be dimethyl carbonate, diethyl carbonate, carbon
At least one of acid propylene ester, ethylene carbonate and acetonitrile.It is preferred that, the solute of electrolyte is LiPF6, solvent is carbonic acid two
The mixed liquor of methyl esters and ethylene carbonate, and the volume ratio of dimethyl carbonate and ethylene carbonate is 1:1, and the concentration of electrolyte
For 0.5~1mol/L.
Wherein, gelatin polymer film is soaked in electrolyte after 30~60 minutes, in addition to dry step：Vacuum is done
60 DEG C are dried in vacuo 12~20 hours in dry case.
Above-mentioned method for preparing gel polymer electrolyte, technique is simple, easy to operate, and production efficiency is high.Prepare
Gel polymer electrolyte decomposition voltage reach 5.1V（vs.Li/Li+）, and with higher electrical conductivity, have with lithium metal
Compatible well, also with wider electrochemical window, i.e., above-mentioned method for preparing gel polymer electrolyte is prepared
Gelatin polymer there is preferable performance.
It is specific embodiment part below：
Embodiment 1
The method for preparing gel polymer electrolyte of the present embodiment is as follows：
（1）Prepare gel polymer electrolyte：It is continuous using rotating speed as 200 revs/min in nitrogen atmosphere and use agitator
Under conditions of stirring, the lauryl sodium sulfate of 1.0 parts by weight is added in the deionized water of 72 parts by weight and dissolved, 0.5 is small
Shi Hou, adds the Butyl Acrylate Monomer of 26.9 parts by weight（BA）, styrene monomer (St), methyl methacrylate monomer
（MMA）And acrylonitrile monemer（AN）, wherein, Butyl Acrylate Monomer（BA）, styrene monomer (St), methyl methacrylate list
Body（MMA）And acrylonitrile monemer（AN）Mass ratio be 1:1:2:4,60 DEG C of insulation reactions are warming up to 0.5 hour, in 60 DEG C of insulations
Under conditions of, the sodium peroxydisulfate solution of 0.1 parts by weight is added dropwise with 1 drop/sec of drop rate with constant pressure funnel, then regulation stirring
The rotating speed of device is 600 revs/min, stirs and in 60 DEG C of insulation reactions 6 hours, obtains milky polymer emulsion.
According to aluminum sulfate（Al2（SO4）3）The aqueous solution volume and the volume ratio 1 of polymer emulsion:1, by polymer breast
Liquid is added to the aluminum sulfate that mass percentage concentration is 2%（Al2（SO4）3）The aqueous solution in stir demulsification, then filtered through suction filtration
Slag, the deionized water by the filter residue first by 40 DEG C is cleaned 4 times, and the washes of absolute alcohol under using normal temperature 5 times then makes
Cleaned with the deionized water under normal temperature 8 times, obtain washed product, the washed product is placed in bellows 45 DEG C of dryings 3 hours,
Then it is transferred in vacuum drying chamber 60 DEG C to be dried in vacuo 12 hours, the gel polymer electrolyte for obtaining the present embodiment polymerize
Thing.
The gel polymer electrolyte of the present embodiment is with the synthetic route of polymer：
（2）At 70 DEG C, by the above-mentioned gel polymer electrolyte of 4 parts by weight with polymer stirring and dissolving in 96 parts by weight
DMF in, obtain viscous solution after being completely dissolved.
（3）Above-mentioned viscous solution is coated on polyethylene using coating machine（PE）On film support, then using coating machine
Drying equipment to being coated the polyethylene of viscous solution（PE）Film support is dried, and is finally coated with viscous solution
Polyethylene（PE）Film support is placed in vacuum drying oven 60 DEG C and is dried in vacuo 12 hours, obtains polyethylene（PE）Film support is supported
Gelatin polymer film.
（4）In the glove box full of nitrogen, by polyethylene（PE）The gelatin polymer film of film support support is placed in hand
Required size is cut into casing, then by polyethylene（PE）The gelatin polymer film of film support support is soaked in electrolyte
30 minutes, obtain polyethylene（PE）The gelatin polymer film gel polymer electrolyte of film support support（GPE）, wherein, electricity
The solute for solving liquid is LiPF6, solvent is the mixed liquor of dimethyl carbonate and ethylene carbonate, and dimethyl carbonate and ethylene carbonate
The volume ratio of ester is 1:1, and LiPF6Concentration be 0.5mol/L.
Above-mentioned gel polymer electrolyte is finally assembled into structure for Li/GPE/LiNi0.5Mn1.5O42025 type buttons
Gel polymer lithium ion battery.
What Fig. 3 was represented is that butyl acrylate, styrene, methyl methacrylate, propylene are fine and manufactured in the present embodiment solidifying
The infared spectrum of xanthan polymer electrolyte polymer.It is known that gel polymer electrolyte manufactured in the present embodiment from Fig. 3
Matter is 1727.9cm with the absworption peak for having C=O stretching vibration peaks in polymer-1, the absworption peak of C ≡ N stretching vibration peaks is
2241.2cm-1, the absworption peak of the stretching vibration peak of phenyl key is 1454.1cm-1, but Butyl Acrylate Monomer（BA）In C=C
The 1639.4cm of stretching vibration peak-1The 1629.8cm of C=C stretching vibration peaks in absworption peak, styrene monomer (St)-1Absorb
Peak, methyl methacrylate monomer（MMA）The 1643.2cm of middle C=C stretching vibration peaks-1Absworption peak and acrylonitrile monemer（AN）
The 1608.6cm of middle C=C stretching vibration peaks-1Absworption peak is disappeared, and shows that the gel polymer electrolyte is with the synthesis of polymer
It is polymerize by opening respective C=C double bonds.
What Fig. 4 was represented is the scanning electron microscope (SEM) photograph of gelatin polymer film manufactured in the present embodiment（SEM）, can from Fig. 4
Go out, the surface of gelatin polymer film is formed with intensive uniform hole, and this some holes weave in, the pore structure of weave in
It is more beneficial for adsorbing electrolyte, so as to be more beneficial for the raising of electrical conductivity.
What Fig. 5 was represented is gel polymer electrolyte AC impedance curve manufactured in the present embodiment.This is implemented during test
Gel polymer electrolyte prepared by example is placed between two stainless steel electrodes, carries out AC impedance experiment.Can from Fig. 5
Go out, be linearly the resistance of the gel polymer electrolyte of the present embodiment with the intersection point of real axis, according to σ=L/AR（L represents solidifying
The thickness of xanthan polymer electrolyte, A is the contact area of stainless steel plate and film, and R is the resistance of polymer dielectric）, calculate
To ionic conductivity σ=3.21 × 10 of gel polymer electrolyte manufactured in the present embodiment at room temperature-3S·cm-1, i.e. this implementation
The gel polymer electrolyte of example has higher electrical conductivity, reaches the requirement of practical application.
What Fig. 6 was represented is the thermogravimetric curve of gelatin polymer film manufactured in the present embodiment（TG）.From Fig. 6 it is known that
Gelatin polymer film manufactured in the present embodiment is all undecomposed in the range of 330 DEG C, that is to say, that gel manufactured in the present embodiment
Polymer film has higher thermodynamic stability, can be with safety applications in lithium ion battery, and can widen lithium-ion electric
The application in pond.
What Fig. 7 was represented is that gel polymer electrolyte manufactured in the present embodiment is assembled into structure for SS/GPE/ with lithium metal
The electrochemical stability window test curve figure of Li battery.Gel polymer electrolyte is determined using linear sweep voltammetry
Electrochemical stability window, learns from Fig. 7, and the electrochemical stability window of gel polymer electrolyte manufactured in the present embodiment is
5.1V（vs.Li/Li+）.
What Fig. 8 was represented is that the gel polymer electrolyte that the present embodiment is prepared is assembled into structure for Li/ with lithium metal
The starting of GPE/Li button cells, the interface resistance figure after five days and after ten days.Wherein, in fig. 8, under high frequency, between semicircle
Diameter be interface resistance, interface resistance is increased over time and increased, and the increase of interface resistance is due to gel polymerisation
The reaction of thing electrolyte and lithium metal, causes the continued propagation of lithium metal surface passivation layer, i.e., gel manufactured in the present embodiment gathers
Polymer electrolyte has good compatibility with lithium metal.In OCP, from 500KHz to 30mHz in the range of and 5mV shake
Battery Li/GPE/Li EIS is measured under width, battery is removed after having surveyed and places 5 at room temperature（Or 10）My god, then in identical
Condition measures battery 5（Or 10）EIS after it.
What Fig. 9 was represented is that the structure of the present embodiment is Li/GPE/LiNi0.5Mn1.5O42025 type button gelatin polymers
The cyclic curve figure of lithium ion battery and traditional liquid lithium ionic cell at 0.5C multiplying powers, 55 DEG C.It can be obtained from Fig. 9
Know, after the circle of circulation 50, the gel polymer lithium ion battery discharge capacity remains 91%, higher than liquid lithium ionic cell
（64%）, and the gel polymer lithium ion battery is under 550 DEG C of hot conditions, shows preferable cyclical stability, also
It is to say, gel polymer electrolyte polymer of the invention can provide possibility for the use of lithium ion battery at high temperature.
Embodiment 2
The method for preparing gel polymer electrolyte of the present embodiment is as follows：
（1）Prepare gel polymer electrolyte：It is continuous using rotating speed as 200 revs/min in argon gas atmosphere and use agitator
Under conditions of stirring, the dodecyl sulphate potassium of 1.5 parts by weight is added in the deionized water of 70 parts by weight and dissolved, 0.5 is small
Shi Hou, adds the Butyl Acrylate Monomer of 28.3 parts by weight（BA）, styrene monomer (St), methyl methacrylate monomer
（MMA）And acrylonitrile monemer（AN）, wherein, Butyl Acrylate Monomer（BA）, styrene monomer (St), methyl methacrylate list
Body（MMA）And acrylonitrile monemer（AN）Mass ratio be 1:1:1:1,58 DEG C of insulation reactions are warming up to 0.3 hour, in 58 DEG C of insulations
Under conditions of, the sodium peroxydisulfate solution of 0.2 parts by weight is added dropwise with 2 drops/sec of drop rate with constant pressure funnel, then regulation stirring
The rotating speed of device is 650 revs/min, stirs and in 58 DEG C of insulation reactions 5 hours, obtains milky polymer emulsion.
According to aluminum sulfate（Al2（SO4）3）The aqueous solution volume and the volume ratio 1.2 of polymer emulsion:1, by polymer
Emulsion is added to the aluminum sulfate that mass percentage concentration is 2%（Al2（SO4）3）The aqueous solution in stir demulsification, then filtered through suction filtration
Slag, the deionized water by the filter residue first by 30 DEG C is cleaned 5 times, and the washes of absolute alcohol under using normal temperature 6 times then makes
Cleaned with the deionized water under normal temperature 9 times, obtain washed product, it is small that the washed product is placed on into 40 DEG C of dryings 2.5 in bellows
When, then it is transferred in vacuum drying chamber 55 DEG C and is dried in vacuo 14 hours, obtains the gel polymer electrolyte of the present embodiment with poly-
Compound：
（2）At 30 DEG C, by the above-mentioned gel polymer electrolyte of 6 parts by weight with polymer stirring and dissolving in 94 parts by weight
Acetone in, obtain viscous solution after being completely dissolved.
（3）Above-mentioned viscous solution is coated on polypropylene screen using coating machine（PP）On supporter, then using coating machine
Drying equipment to being coated the polypropylene screen of viscous solution（PP）Supporter is dried, and is finally coated with viscous solution
Polypropylene screen（PP）Supporter is placed in vacuum drying oven 60 DEG C and is dried in vacuo 14 hours, obtains polypropylene screen（PP）Support body supports
Gelatin polymer film.
（4）In the glove box full of argon gas, by polypropylene screen（PP）The gelatin polymer film of support body supports is placed in hand
Required size is cut into casing, then by polypropylene screen（PP）The gelatin polymer film of support body supports is soaked in electrolyte
35 minutes, obtain polypropylene screen（PP）The gelatin polymer film gel polymer electrolyte of support body supports（GPE）, wherein, electricity
The solute for solving liquid is LiBF4, solvent is diethyl carbonate, and LiBF4Concentration be 1mol/L.
Above-mentioned gel polymer electrolyte is finally assembled into structure for Li/GPE/LiNi0.5Mn1.5O42025 type buttons
Gel polymer lithium ion battery.
Embodiment 3
The method for preparing gel polymer electrolyte of the present embodiment is as follows：
（1）Prepare gel polymer electrolyte：It is continuous using rotating speed as 200 revs/min in helium atmosphere and use agitator
Under conditions of stirring, the ammonium lauryl sulfate of 2 parts by weight is added in the deionized water of 64.4 parts by weight and dissolved, 0.5 is small
Shi Hou, adds the Butyl Acrylate Monomer of 29.7 parts by weight（BA）, styrene monomer (St), methyl methacrylate monomer
（MMA）And acrylonitrile monemer（AN）, wherein, Butyl Acrylate Monomer（BA）, styrene monomer (St), methyl methacrylate list
Body（MMA）And acrylonitrile monemer（AN）Mass ratio be 1:1:1:4,62 DEG C of insulation reactions are warming up to 0.4 hour, in 62 DEG C of insulations
Under conditions of, the sodium peroxydisulfate solution of 0.3 parts by weight is added dropwise with 2 drops/sec of drop rate with constant pressure funnel, then regulation stirring
The rotating speed of device is 700 revs/min, stirs and in 62 DEG C of insulation reactions 5.5 hours, obtains milky polymer emulsion.
According to aluminum sulfate（Al2（SO4）3）The aqueous solution volume and the volume ratio 1.5 of polymer emulsion:1, by polymer
Emulsion is added to the aluminum sulfate that mass percentage concentration is 2%（Al2（SO4）3）The aqueous solution in stir demulsification, then filtered through suction filtration
Slag, the deionized water by the filter residue first by 32 DEG C is cleaned 6 times, and the washes of absolute alcohol under using normal temperature 7 times then makes
Cleaned with the deionized water under normal temperature 10 times, obtain washed product, it is small that the washed product is placed on into 42 DEG C of dryings 2.4 in bellows
When, then it is transferred in vacuum drying chamber 57 DEG C and is dried in vacuo 16 hours, obtains the gel polymer electrolyte of the present embodiment with poly-
Compound：
（2）At 35 DEG C, by the above-mentioned gel polymer electrolyte of 6 parts by weight with polymer stirring and dissolving in 94 parts by weight
Tetrahydrofuran in, obtain viscous solution after being completely dissolved.
（3）Above-mentioned viscous solution is coated on PP-PE-PP supporters using coating machine, then using the dry of coating machine
Dry equipment is dried to the PP-PE-PP supporters for being coated viscous solution, is finally coated with the PP-PE-PP of viscous solution
Supporter is placed in vacuum drying oven 60 DEG C and is dried in vacuo 16 hours, obtains the gelatin polymer film of PP-PE-PP support body supports.
（4）In the glove box full of argon gas, the gelatin polymer film of PP-PE-PP support body supports is placed in glove box
In be cut into required size, then the gelatin polymer film of PP-PE-PP support body supports is soaked in electrolyte 40 minutes,
Obtain the gelatin polymer film gel polymer electrolyte of PP-PE-PP support body supports（GPE）, wherein, the solute of electrolyte is
LiPF6, solvent is dimethyl carbonate（DMC）And ethylene carbonate（EC）Mixed liquor, and dimethyl carbonate（DMC）And ethylene
Alkene ester（EC）Volume ratio be 1:1, and LiPF6Concentration be 1mol/L.
Above-mentioned gel polymer electrolyte is finally assembled into structure for Li/GPE/LiNi0.5Mn1.5O42025 type buttons
Gel polymer lithium ion battery.
Embodiment 4
The method for preparing gel polymer electrolyte of the present embodiment is as follows：
（1）Prepare gel polymer electrolyte：It is continuous using rotating speed as 200 revs/min in argon gas atmosphere and use agitator
Under conditions of stirring, the dodecyl sulphate potassium of 2.5 parts by weight is added in the deionized water of 62.1 parts by weight and dissolved, 0.5
After hour, the Butyl Acrylate Monomer of 31.1 parts by weight is added（BA）, styrene monomer (St), methyl methacrylate monomer
（MMA）And acrylonitrile monemer（AN）, wherein, Butyl Acrylate Monomer（BA）, styrene monomer (St), methyl methacrylate list
Body（MMA）And acrylonitrile monemer（AN）Mass ratio be 1:2:2:4,65 DEG C of insulation reactions are warming up to 0.5 hour, in 65 DEG C of insulations
Under conditions of, the sodium peroxydisulfate solution of 0.4 parts by weight is added dropwise with 1 drop/sec of drop rate with constant pressure funnel, then regulation stirring
The rotating speed of device is 750 revs/min, stirs and in 65 DEG C of insulation reactions 6.5 hours, obtains milky polymer emulsion.
According to aluminum sulfate（Al2（SO4）3）The aqueous solution volume and the volume ratio 1.7 of polymer emulsion:1, by polymer
Emulsion is added to the aluminum sulfate that mass percentage concentration is 2%（Al2（SO4）3）The aqueous solution in stir demulsification, then filtered through suction filtration
Slag, the deionized water by the filter residue first by 38 DEG C is cleaned 5 times, and the washes of absolute alcohol under using normal temperature 7 times then makes
Cleaned with the deionized water under normal temperature 10 times, obtain washed product, it is small that the washed product is placed on into 45 DEG C of dryings 2.6 in bellows
When, then it is transferred in vacuum drying chamber 55 DEG C and is dried in vacuo 18 hours, obtains the gel polymer electrolyte of the present embodiment with poly-
Compound：
（2）At 75 DEG C, by the above-mentioned gel polymer electrolyte of 8 parts by weight with polymer stirring and dissolving in 92 parts by weight
DMF in, obtain viscous solution after being completely dissolved.
（3）Above-mentioned viscous solution is coated on PE supporters using coating machine, then using the drying equipment of coating machine
The PE supporters for being coated viscous solution are dried, the PE supporters for being finally coated with viscous solution are placed in vacuum drying oven
In 60 DEG C be dried in vacuo 16 hours, obtain the gelatin polymer film of PE support body supports.
（4）In the glove box full of argon gas, the gelatin polymer film of PE support body supports is placed in glove box and cut
Into required size, then the gelatin polymer film of PE support body supports is soaked in electrolyte 45 minutes, PE supporters are obtained
The gelatin polymer film gel polymer electrolyte of support（GPE）, wherein, the solute of electrolyte is LiN (SO2CF3)2, solvent is
The mixed liquor of propene carbonate, ethylene carbonate and acetonitrile, and the volume ratio of propene carbonate, ethylene carbonate and acetonitrile is
0.5:1:0.5, and LiN (SO2CF3)2Concentration be 0.5mol/L.
Above-mentioned gel polymer electrolyte is finally assembled into structure for Li/GPE/LiNi0.5Mn1.5O42025 type buttons
Gel polymer lithium ion battery.
Embodiment 5
The method for preparing gel polymer electrolyte of the present embodiment is as follows：
（1）Prepare gel polymer electrolyte：Constantly stirred using rotating speed as 200/ minute in argon gas atmosphere and using agitator
Under conditions of mixing, the ammonium lauryl sulfate of 3 parts by weight is added in the deionized water of 64 parts by weight and dissolved, after 0.5 hour,
Add the Butyl Acrylate Monomer of 32.5 parts by weight（BA）, styrene monomer (St), methyl methacrylate monomer（MMA）With third
Alkene nitrile monomer（AN）, wherein, Butyl Acrylate Monomer（BA）, styrene monomer (St), methyl methacrylate monomer（MMA）With
Acrylonitrile monemer（AN）Mass ratio be 2:1:2:4, it is warming up to 65 DEG C of insulation reactions 0.5 hour, under conditions of 65 DEG C are incubated,
The sodium peroxydisulfate solution of 0.4 parts by weight is added dropwise with 1 drop/sec of drop rate with constant pressure funnel, the rotating speed of agitator is then adjusted
For 800 revs/min, stir and in 65 DEG C of insulation reactions 7 hours, obtain milky polymer emulsion.
According to aluminum sulfate（Al2（SO4）3）The aqueous solution volume and the volume ratio 1.9 of polymer emulsion:1, by polymer
Emulsion is added to the aluminum sulfate that mass percentage concentration is 2%（Al2（SO4）3）The aqueous solution in stir demulsification, then filtered through suction filtration
Slag, the deionized water by the filter residue first by 42 DEG C is cleaned 6 times, and the washes of absolute alcohol under using normal temperature 8 times then makes
Cleaned with the deionized water under normal temperature 9 times, obtain washed product, it is small that the washed product is placed on into 50 DEG C of dryings 2.8 in bellows
When, then it is transferred in vacuum drying chamber 58 DEG C and is dried in vacuo 20 hours, obtains the gel polymer electrolyte of the present embodiment with poly-
Compound：
（2）At 30 DEG C, by the above-mentioned gel polymer electrolyte of 10 parts by weight with polymer stirring and dissolving in 90 weight
In the acetone of part, viscous solution is obtained after being completely dissolved.
（3）Above-mentioned viscous solution is coated on PP supporters using coating machine, then using the drying equipment of coating machine
The PP supporters for being coated viscous solution are dried, the PP supporters for being finally coated with viscous solution are placed in vacuum drying oven
In 60 DEG C be dried in vacuo 20 hours, obtain the gelatin polymer film of PP support body supports.
（4）In the glove box full of argon gas, the gelatin polymer film of PP support body supports is placed in glove box and cut
Into required size, then the gelatin polymer film of PP support body supports is soaked in electrolyte 45 minutes, PP supporters are obtained
The gelatin polymer film gel polymer electrolyte of support（GPE）, wherein, the solute of electrolyte is LiN (SO2F)2, solvent is carbon
The mixed liquor of dimethyl phthalate and ethylene carbonate, and the volume ratio of dimethyl carbonate and ethylene carbonate is 1:1, and LiN
(SO2F)2Concentration be 1mol/L.
Above-mentioned gel polymer electrolyte is finally assembled into structure for Li/GPE/LiNi0.5Mn1.5O42025 type buttons
Gel polymer lithium ion battery.
Embodiment 6
The method for preparing gel polymer electrolyte of the present embodiment is as follows：
（1）Prepare gel polymer electrolyte：It is continuous using rotating speed as 200 revs/min in nitrogen atmosphere and use agitator
Under conditions of stirring, the dodecyl sulphate potassium of 3 parts by weight is added in the deionized water of 60 parts by weight and dissolved, 0.5 hour
Afterwards, the Butyl Acrylate Monomer of 36.51 parts by weight is added（BA）, styrene monomer (St), methyl methacrylate monomer（MMA）
And acrylonitrile monemer（AN）, wherein, Butyl Acrylate Monomer（BA）, styrene monomer (St), methyl methacrylate monomer
（MMA）And acrylonitrile monemer（AN）Mass ratio be 2:1:4:4,65 DEG C of insulation reactions are warming up to 0.5 hour, in 65 DEG C of insulations
Under the conditions of, the sodium peroxydisulfate solution of 0.5 parts by weight is added dropwise with 1 drop/sec of drop rate with constant pressure funnel, agitator is then adjusted
Rotating speed be 850 revs/min, stir and in 65 DEG C of insulation reactions 8 hours, obtain milky polymer emulsion.
According to aluminum sulfate（Al2（SO4）3）The aqueous solution volume and the volume ratio 2 of polymer emulsion:1, by polymer breast
Liquid is added to the aluminum sulfate that mass percentage concentration is 5%（Al2（SO4）3）The aqueous solution in stir demulsification, then filtered through suction filtration
Slag, the deionized water by the filter residue first by 50 DEG C is cleaned 5 times, and the washes of absolute alcohol under using normal temperature 8 times then makes
Cleaned with the deionized water under normal temperature 10 times, obtain washed product, it is small that the washed product is placed on into 50 DEG C of dryings 3 in bellows
When, then it is transferred in vacuum drying chamber 59 DEG C and is dried in vacuo 22 hours, obtains the gel polymer electrolyte of the present embodiment with poly-
Compound：
（2）At 70 DEG C, by the above-mentioned gel polymer electrolyte of 12 parts by weight with polymer stirring and dissolving in 88 weight
In the DMF of part, viscous solution is obtained after being completely dissolved.
（3）Above-mentioned viscous solution is coated on PE supporters using coating machine, then using the drying equipment of coating machine
The PE supporters for being coated viscous solution are dried, the PE supporters for being finally coated with viscous solution are placed in vacuum drying oven
In 60 DEG C be dried in vacuo 24 hours, obtain the gelatin polymer film of PE support body supports.
（4）In the glove box full of argon gas, the gelatin polymer film of PE support body supports is placed in glove box and cut
Into required size, then the gelatin polymer film of PE support body supports is soaked in electrolyte 60 minutes, PE supporters are obtained
The gelatin polymer film gel polymer electrolyte of support（GPE）, wherein, the solute of electrolyte is LiPF6, solvent is carbonic acid two
The mixed liquor of methyl esters and ethylene carbonate, and the volume ratio of dimethyl carbonate and ethylene carbonate is 1:1, and LiPF6Concentration
For 1mol/L.
Above-mentioned gel polymer electrolyte is finally assembled into structure for Li/GPE/LiNi0.5Mn1.5O42025 type buttons
Gel polymer lithium ion battery.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (4)
1. a kind of preparation method of gel polymer electrolyte polymer, it is characterised in that comprise the following steps：
Under conditions of being stirred continuously using rotating speed as 200 revs/min in nitrogen atmosphere and using agitator, by the ten of 1.0 parts by weight
Sodium dialkyl sulfate, which is added in the deionized water of 72 parts by weight, to be dissolved, and after 0.5 hour, adds the acrylic acid fourth of 26.9 parts by weight
Ester monomer, styrene monomer, methyl methacrylate monomer and acrylonitrile monemer, wherein, Butyl Acrylate Monomer, styrene list
The mass ratio of body, methyl methacrylate monomer and acrylonitrile monemer is 1:1:2:4, it is warming up to 60 DEG C of insulation reactions 0.5 hour,
Under conditions of 60 DEG C are incubated, the sodium peroxydisulfate solution of 0.1 parts by weight is added dropwise with 1 drop/sec of drop rate with constant pressure funnel, so
The rotating speed of regulation agitator is 600 revs/min afterwards, stirs and in 60 DEG C of insulation reactions 6 hours, obtains milky polymer breast
Liquid；
According to the volume and the volume ratio 1 of polymer emulsion of the aqueous solution of aluminum sulfate:1, polymer emulsion is added to quality hundred
Divide concentration to stir demulsification in the aqueous solution of 2% aluminum sulfate, then filter residue is obtained through suction filtration, by the filter residue first by 40 DEG C
Deionized water is cleaned 4 times, the washes of absolute alcohol under using normal temperature 5 times, then using the deionized water cleaning 8 under normal temperature
It is secondary, washed product is obtained, the washed product is placed in bellows 45 DEG C of dryings 3 hours, is then transferred to 60 in vacuum drying chamber
DEG C vacuum drying 12 hours, obtain the gel polymer electrolyte polymer with following structural formula：
Wherein, n is 9800.
2. the gel that a kind of gel polymer electrolyte as claimed in claim 1 is prepared with the preparation method of polymer gathers
Polymer electrolyte polymer.
3. a kind of method for preparing gel polymer electrolyte, it is characterised in that comprise the following steps：
According to the gel polymer electrolyte described in claim 1 gel polymer electrolyte is prepared with the preparation method of polymer
Use polymer；
At 70 DEG C, by the above-mentioned gel polymer electrolyte of 4 parts by weight with polymer stirring and dissolving in the N of 96 parts by weight, N-
In dimethylformamide, viscous solution is obtained after being completely dissolved；
Above-mentioned viscous solution is coated on polyethylene film supporter using coating machine, then using the drying equipment pair of coating machine
The polyethylene film supporter for being coated viscous solution is dried, and the polyethylene film supporter for being finally coated with viscous solution is put
60 DEG C are dried in vacuo 12 hours in vacuum drying oven, obtain the gelatin polymer film of polyethylene film support body supports；
In the glove box full of nitrogen, the gelatin polymer film of polyethylene film support body supports is placed in glove box and is cut into
The gelatin polymer film of polyethylene film support body supports, is then soaked in electrolyte 30 minutes, obtains poly- second by required size
The gelatin polymer film gel polymer electrolyte of alkene film support support, wherein, the solute of electrolyte is LiPF6, solvent is
The mixed liquor of dimethyl carbonate and ethylene carbonate, and the volume ratio of dimethyl carbonate and ethylene carbonate is 1:1, and LiPF6
Concentration be 0.5mol/L.
4. the gel polymer electrolyte that a kind of method for preparing gel polymer electrolyte as claimed in claim 3 is prepared
Matter.
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| KR102255536B1 (en) * | 2017-11-30 | 2021-05-25 | 주식회사 엘지에너지솔루션 | Composition for gel polymer electrolyte, gel polymer electrolyte and lithium secondary battery comprising the same |
| CN110112009B (en) * | 2019-05-31 | 2021-06-01 | 广州大学 | Capacitor composite electrolyte and preparation method and application thereof |
| CN111613832B (en) * | 2020-04-21 | 2023-06-02 | 浙江锋锂新能源科技有限公司 | Pentad monomer copolymer lithium secondary battery and preparation method thereof |
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| CN101747642A (en) * | 2008-12-05 | 2010-06-23 | 比亚迪股份有限公司 | Gel polymer electrolyte, polymer battery and preparing method |
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| CN101409365A (en) * | 2008-11-19 | 2009-04-15 | 华南师范大学 | Lithium ion battery gel polymer electrolyte doped with nanometer particle and preparation method thereof |
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