CN105932329A - Gel polymer electrolyte membrane and preparation method and application thereof - Google Patents
Gel polymer electrolyte membrane and preparation method and application thereof Download PDFInfo
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- CN105932329A CN105932329A CN201610508516.6A CN201610508516A CN105932329A CN 105932329 A CN105932329 A CN 105932329A CN 201610508516 A CN201610508516 A CN 201610508516A CN 105932329 A CN105932329 A CN 105932329A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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Abstract
The invention belongs to the field of lithium ion batteries, and specifically discloses a gel polymer electrolyte membrane and a preparation method and an application thereof. The preparation method comprises the steps of: firstly, performing emulsion polymerization by a n-butyl methacrylate monomer, an acrylonitrile monomer and a styrene monomer of different proportions to obtain a copolymer; secondly, under an ultrasonic condition, dispersing a certain amount of nano particles in a solvent for a period of time, dissolving a polymer powder into the solvent to obtain a sticky gel, and then obtaining a gel polymer ceramic membrane through a phase-transfer method; and finally, soaking the membrane into electrolyte, then a gel polymer electrolyte is obtained. The gel polymer electrolyte provided by the invention is high in safety performance, strong in ability to absorb the electrolyte, and high in electrochemical stability window; after being assembled into a button cell, through a circulation of 150 weeks, 93% of an initial capacity can still be maintained. The preparation process of the invention is very simple and the raw materials are cheap and easily available; and the invention provides a gel electrolyte which can be directly used to a polymer lithium ion battery, which is convenient for industrial production.
Description
Technical field
The invention belongs to field of lithium ion battery, be specifically related to a kind of gel polymer electrolyte barrier film and system thereof
Preparation Method and application.
Background technology
Compared to conventional batteries, secondary lithium battery have have extended cycle life, energy density is high, volume is light
Just, the advantage such as memory-less effect, environmental friendliness, be widely used in little to blue-tooth device, big to storage
In the power such as energy power station and energy storage device, and with inundant speed fast development.But at mesh
In front business-like lithium ion battery, it is the liquid electrolyte using carbonic acid lipid organic solvent greatly.
Although liquid electrolyte has a highest lithium ion conductivity, but the low-flash of itself, low-steam pressure,
The physical characteristic such as inflammable, determines and uses the lithium ion battery of liquid electrolyte to there is the biggest potential safety hazard,
Particularly use in relatively harsh environment.In numerous solutions, use liquid electrolyte (high
Electrical conductivity) and the perfect incarnation gel polymer electrolyte (GPE) of solid electrolyte (high security)
It it is a kind of method more satisfactory and easy to implement.GPE is by polymeric matrix absorption liquid electrolyte
Form gel state electrolyte, the random mobile of liquid electrolyte can be prevented effectively from.Because of gelatin polymer matrix
And the gelling between electrolyte, effectively reduces the electro-chemical activity of liquid electrolyte, improves GPE
Electrochemical decomposition voltage, therefore, GPE goes in high-voltage lithium ion batteries.Have very at present
How about the report of polymer of GPE matrix, as Kynoar (PVDF), polyacrylonitrile (PAN),
Polymethyl methacrylate (PMMA), polyethylene glycol oxide (PEO), polyvinyl chloride (PVC) etc..But
Owing to using same monomers to be polymerized, there are some defects: mechanicalness during ionic conductivity height in these matrixes
Can be bad, during mechanical strength height, ionic conductivity is low.
The Chinese invention patent of Application No. 200710025612.6 discloses that " a kind of semi-interpenetrating network gel gathers
The preparation method of polymer electrolyte film ", but electrochemical stability window is the most not ideal, only 4.6V (vs.
Li/Li+), Applicable temperature scope is the narrowest.The Chinese invention patent of Application No. 200610043125.8 is open
" one-step method causes polymerization to prepare nano silicon dioxide/polymethyl methacrylate gel polymer dielectric
Method ", although mechanical strength is more satisfactory, but ionic conductivity is the most not ideal enough, and only up to 3.44 × 10-4
S·cm-1。
Summary of the invention
In place of shortcoming and defect for solution prior art, the primary and foremost purpose of the present invention is to provide a kind of gel
The preparation method of polymer electrolyte diaphragm.
Another object of the present invention is to provide a kind of electrochemical stability prepared by above-mentioned preparation method good,
The gel polymer electrolyte barrier film that ionic conductivity is high, security performance is high.
It is still another object of the present invention to provide above-mentioned gel polymer electrolyte barrier film and prepare gelatin polymer
Application in lithium ion battery.
Present invention also offers a kind of lithium ion using above-mentioned height safe gel polymer electrolyte barrier film to prepare
Battery.
The object of the invention is achieved through the following technical solutions:
The preparation method of a kind of gel polymer electrolyte barrier film, comprises the steps:
(1) prepare polymer: under inert protective atmosphere is enclosed, by 1～4% emulsifying agent join 60～72%
In ionized water after stirring and dissolving, addition 25～38% monomer methacrylic acid N-butyl (BMA), acrylonitrile (AN)
With styrene (St), temperature is increased to 55～65 DEG C simultaneously；Addition 0.1～0.4% initiator, control 20～50
Minute add initiator, after continuously stirring 4～10 hours, obtain egg white shape emulsion；Pour egg white shape emulsion into matter
Amount mark is the Al of 2～5%2(SO4)3Solution stirs breakdown of emulsion, then uses deionized water and absolute ethyl alcohol repeatedly
Clean, obtain white polymer；Again white polymer is vacuum dried；Above-mentioned percentage is percent mass
Ratio, wherein the mass percent sum of emulsifying agent, deionized water, monomer and initiator is 100%；
(2) gelatin polymer film is prepared: with ultrasonic disperser by nano particle ultrasonic disperse in 89～95%
Organic solvent in, controlling ultrasonic time is 20～40 minutes, adds 4～the step of 10% after being uniformly dispersed
(1) white polymer prepared, the quality of above-mentioned nano particle is the 0～20% of white polymer quality, machine
The viscous fluid of water white transparency or white is obtained after tool stirring 1～3h；The viscous solution obtained is uniformly coated on and props up
The two sides of support body, then be dipped in de-ionized water tank initiation phase transfer, after the film obtained is dried in the air at normal temperatures
Dry, vacuum drying, prepare lithium ion battery gelatin polymer film；Above-mentioned percentage is quality hundred
Proportion by subtraction, wherein the mass percent sum of organic solvent, white polymer and nano particle is 100%；
(3) prepare gel polymer electrolyte barrier film: in glove box, by step (2) prepare lithium from
After sub-battery gelatin polymer film soaks 0.5～1 hour in the electrolytic solution, obtain lithium ion battery gel and gather
Polymer electrolyte barrier film.
In step (1), described inert atmosphere is nitrogen (N2) or argon gas (Ar) atmosphere；Described emulsification
Agent is lauryl sodium sulfate, dodecyl sulphate potassium or ammonium lauryl sulfate；Described monomer metering system
Acid N-butyl, acrylonitrile and cinnamic mass ratio are 1～4:1～2:1～8；Described mixing speed is
600～1000r/min；Described initiator is sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate；Described Al2(SO4)3
The solvent quality of solution is equal to the gross mass of egg white shape emulsion；Described vacuum drying temperature is 50～70 DEG C,
Time is 12～36 hours.
In step (2), described organic solvent forms transparent and homogeneous thickness for can effectively dissolve above-mentioned polymer
The organic solvent of liquid, but it is not limited to the one in DMF, acetone, oxolane or many
Plant the organic solvent of mixing；Described nano particle is SiO2、Al2O3、SnO2、TiO2、LiAlO2、CeO2、
Fe3O4, rare earth, clay or zeolite；Described supporter be polyethylene film, polypropylene screen, polypropylene-ethylene-
One in propylene sandwich diaphragm；The thickness of described lithium ion battery gel polymer film is 40 μm～80 μm；
Described vacuum drying temperature is 50～60 DEG C, and the time is 24～36 hours.
In step (3), described electrolyte is by lithium hexafluoro phosphate (LiPF6), ethylene carbonate (EC), carbon
Dimethyl phthalate (DMC) and methyl ethyl carbonate (EMC) composition, wherein EC:DMC:EMC mass ratio
It is 1～2:1～2:1, LiPF6Molar concentration be 0.5～1.5mol/L
Gel polymer electrolyte lithium-ion prepared by above-mentioned lithium ion battery gel polymer electrolyte barrier film
Application in battery, specifically comprises the following steps that in glove box, is put by above-mentioned gel polymer electrolyte barrier film
Between positive pole diaphragm and cathode membrane, it is assembled into gel polymer electrolyte lithium-ion battery.
The active material of described positive pole diaphragm is cobalt acid lithium, LiMn2O4, lithium nickelate, nickel ion doped, nickel cobalt manganese
Acid lithium or LiFePO4；The active material of described cathode membrane is Delanium, native graphite, mesocarbon
Microballoon, mesophase carbon fiber, soft carbon, hard carbon or metal lithium sheet；Described gel polymer electrolyte lithium-ion
Battery is button cell or soft-package battery.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) present invention is raw materials used is easy to get, with low cost, and preparation technology is simple, and production efficiency is high, preparation
Technology is mutually compatible with the Preparation equipment of existing lithium ion battery, it is simple to Industry Promotion and application.
(2) solvent used by the present invention is deionized water, is not related to the organic solvent of effumability, meets green
Look environmental protection concept.
(3) the gel polymer electrolyte barrier film that prepared by the present invention possesses good imbibition ability, ionic conductance
Rate and electrochemical stability window are improved significantly, without the conductivity at room temperature adding nano particle
It is 1.44 × 10-3S·cm-1, electrochemical stability window is 4.9V (vs.Li/Li+), with the addition of nano silicon
The conductivity at room temperature of particle is up to 1.87 × 10-3S·cm-1, electrochemical stability window is up to 5.2V (vs.
Li/Li+), and the button cell assembled have excellence stable circulation performance, commercial applications can be met
Demand.
Accompanying drawing explanation
Fig. 1 be the polymer film that reference example of the present invention, reference examples and embodiment 1 prepare pick up with
Time changing curve.
Fig. 2 is that the polymer dielectric for preparing of reference example of the present invention, reference examples and embodiment 1 is stainless
Linear scan curve on steel plate；Sweep speed: 1mV s-1。
Fig. 3 is for using different electrolyte at LiNi0.5Mn1.5O4The cyclical stability figure of positive electrode；Test-strips
Part: room temperature, 0.2C electric current, 3.0～4.9V voltage ranges.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but the embodiment party of the present invention
Formula is not limited to this.If no special instructions, the percentage described in following example is mass percent.
Embodiment 1
(1) at N2Under protective atmosphere protection, the emulsifier sodium lauryl sulfate of 1.48% is joined 68.86%
Deionized water in, mechanical agitation is allowed to fully dissolve for 20 minutes, adds the monomer metering system of 29.51%
Acid N-butyl, acrylonitrile and styrene (wherein n-BMA, acrylonitrile and cinnamic quality
Ratio is 1:2:1), temperature is increased to 60 DEG C, mechanical agitation is allowed to mix for 20 minutes.To stir again
Mix device rotating speed and be adjusted to 800r/min, be slowly added dropwise the initiator sodium peroxydisulfate of 0.15% simultaneously by constant pressure funnel,
Within 30 minutes, add initiator.Obtain egg white shape white emulsion after reacting 8 hours, pour emulsion into mass fraction
It is the Al of 3%2(SO4)3The beaker of solution stirs breakdown of emulsion (wherein Al2(SO4)3The solvent quality of solution with should
The gross mass equivalent of emulsion), repeatedly clean with deionized water and absolute ethyl alcohol the most again, suction filtration, until filtrate
In do not have foam and turbid phenomenon to produce till, the polymer of i.e. available white；White polymer will be obtained
It is placed in vacuum drying chamber and is dried 36 hours at 60 DEG C.Wherein emulsifying agent, deionized water, monomer and initiator
Mass percent sum be 100%.
(2) at room temperature, with ultrasonic disperser, the nanometer silicon dioxide particle of 0.70% (is equivalent to white
The 10% of look polymer quality) ultrasonic disperse in the DMF of 92.3%, control ultrasonic
Time is 40 minutes, adds the above-mentioned white polymer of 7% afterwards, mechanical agitator is adjusted to 300r/min,
Viscous fluid is obtained after continuously stirring 2 hours at 80 DEG C, then with stainless steel scraper by uniform for the viscous fluid obtained
It is coated on polyethylene diagrams two sides, then barrier film is immersed in de-ionized water tank, by barrier film from water after 4 hours
In remove, dry at normal temperatures, proceed in vacuum drying chamber to be dried 36 hours at 60 DEG C, thus obtain lithium from
Sub-battery gelatin polymer film, the thickness of this film is 50 μm；Wherein organic solvent N, N-dimethyl formyl
The mass percent sum of amine, white polymer and nanometer silicon dioxide particle is 100%.
(3) in glove box, after above-mentioned gelatin polymer film is cut into required size, it is immersed in electrolyte
(1mol/L LiPF6+ EC+DMC+EMC, EC:DMC:EMC mass ratio is 1:1:1), 0.5
After hour, obtain lithium ion battery gel polymer electrolyte barrier film.
(4) in glove box, with nickel ion doped as positive electrode active materials, with lithium sheet as negative pole, gel is gathered
Polymer electrolyte barrier film is placed between positive pole and negative pole, is assembled into button cell.
Reference examples:
Except not adding any nano particle in step (2), other steps are same as in Example 1.
Reference example:
In glove box, with nickel ion doped as positive electrode active materials, with lithium sheet as negative pole, by polyethylene diagrams
It is placed between positive pole and negative pole, barrier film drips electrolyte (1mol/L LiPF6+ EC+DMC+EMC,
EC:DMC:EMC mass ratio is 1:1:1), it is assembled into button cell.
Test case:
1, in embodiment 1, reference examples, reference example, the pick up of the polymer film prepared becomes in time
The trend changed, as shown in Figure 1.During test, take after polymer film is dipped into liquid electrolyte a period of time
Go out, then siphon away the electrolyte of excess surface with filter paper gently, formula below be calculated gelatin polymer
The pick up of electrolyte: A (%)=(W2-W1)/W1× 100% (wherein W2Represent gel polymer electrolyte
Quality after matter Electolyte-absorptive, W1Quality for before polymer film Electolyte-absorptive).It will be seen that three
Kind polymer film is along with the increase of soak time, and the pick up of electrolyte also increases, and reaches the most after 30 minutes
Maximum.Wherein, the maximum pick up of the gel polymer electrolyte that embodiment 1 obtains reaches 260%, and
The pick up of the electrolyte not adding nano particle that reference examples preparation reaches is 210%, the imbibition of reference example
Rate only has 120%.High pick up ensure that gel polymer electrolyte has high lithium ion conductivity.
2, electrochemical stability window test；
The lithium ion battery gel polymer electrolyte that embodiment 1 and reference examples, reference example obtain is assembled into
Button cell, its structure is Li/ gel polymer electrolyte/stainless steel substrates (SS), carries out electrochemical stability window
Mouth test.Use linear sweep voltammetry to determine the electrochemical stability window of gel polymer electrolyte, survey
The curve that examination obtains is as shown in Figure 2.Visible, prepared by the present invention does not has the gel of the nano particle added to gather
The electrochemical stability window 4.9V of polymer electrolyte, and that the embodiment 1 adding nano particle prepares is solidifying
Xanthan polymer electrolyte has higher electrochemical stability window, for 5.42V (vs.Li/Li+), obviously higher than biography
The decomposition voltage (decomposition voltage of reference example is only 4.4V) of the electrolyte of system.
3, circulating battery stability test；
The lithium ion battery gel polymer electrolyte that embodiment 1 and reference examples, reference example obtain is assembled into
Button cell, its structure is negative pole (Li)/gel polymer electrolyte/positive pole (LiNi0.5Mn1.5O4), carry out
Circulating battery stability test.The condition of button cell test is: room temperature, 0.2C electric current, 3.0～4.9V electricity
Pressure scope.The curve that test obtains is as shown in Figure 3.Visible, prepared by the present invention does not has the nanoparticle of interpolation
The gel polymer electrolyte of son, after circulation 150 weeks, keeps initial capacity 92.3%, and adds nano particle
The gel polymer electrolyte for preparing of embodiment 1 have higher capability retention 93%, all substantially high
Cyclical stability in traditional electrolyte (after reference example circulates 150 weeks, only maintains initial capacity
87.9%).
Embodiment 2
(1) under Ar protective atmosphere is protected, the emulsifying agent dodecyl sulphate potassium of 1% is joined 72%
In deionized water, mechanical agitation is allowed to fully dissolve for 30 minutes, adds the monomer methacrylic acid of 26.9%
N-butyl, acrylonitrile and styrene (wherein n-BMA, acrylonitrile and cinnamic mass ratio
For 1:1:1), temperature is increased to 55 DEG C, mechanical agitation is allowed to mix for 20 minutes.Again will stirring
Device rotating speed is adjusted to 900r/min, is slowly added dropwise the initiator potassium persulfate of 0.1% simultaneously by constant pressure funnel, controls
Within 30 minutes, add initiator.Obtain egg white shape white emulsion after reacting 8 hours, pour emulsion into mass fraction
It is the Al of 2%2(SO4)3The beaker of solution stirs breakdown of emulsion (wherein Al2(SO4)3The solvent quality of solution with should
The gross mass equivalent of emulsion), repeatedly clean with deionized water and absolute ethyl alcohol the most again, suction filtration, until filtrate
In do not have foam and turbid phenomenon to produce till, the polymer of i.e. available white；White polymer will be obtained
It is placed in vacuum drying chamber and is dried 36 hours at 50 DEG C.Wherein emulsifying agent, deionized water, monomer and initiator
Mass percent sum be 100%.
(2) at room temperature, with ultrasonic disperser, the nano-aluminium oxide particle of 0.70% (is equivalent to
The 10% of white polymer quality) ultrasonic disperse is in the DMF of 92.3%, and control is super
The sound time is 30 minutes, adds the above-mentioned white polymer of 7% afterwards, mechanical agitator is adjusted to 400r/min,
Viscous fluid is obtained after continuously stirring 1 hour at 80 DEG C, then with stainless steel scraper by uniform for the viscous fluid obtained
It is coated on polyethylene diagrams two sides, then barrier film is immersed in de-ionized water tank, by barrier film from water after 4 hours
In remove, dry at normal temperatures, proceed in vacuum drying chamber to be dried 36 hours at 50 DEG C, thus obtain lithium from
Sub-battery gelatin polymer film, the thickness of this film is 40 μm；Wherein organic solvent N, N-dimethyl formyl
The mass percent sum of amine, white polymer and nano-aluminium oxide particle is 100%.
(3) in glove box, after above-mentioned gelatin polymer film is cut into required size, it is immersed in electrolyte
(1mol/L LiPF6+ EC+DMC+EMC, EC:DMC:EMC mass ratio is 2:2:1), 1 is little
Shi Hou, obtains lithium ion battery gel polymer electrolyte barrier film.
(4) in glove box, with cobalt acid lithium as positive electrode active materials, with graphite as negative pole, by gel polymerisation
Thing electrolyte membrance is placed between positive pole and negative pole, is assembled into button cell.
Embodiment 3
(1) under Ar protective atmosphere is protected, the emulsifying agent ammonium lauryl sulfate of 4% is joined 60%
In deionized water, mechanical agitation is allowed to fully dissolve for 40 minutes, adds the monomer methacrylic acid of 35.6%
N-butyl, acrylonitrile and styrene (wherein n-BMA, acrylonitrile and cinnamic mass ratio
For 2:1:4), temperature is increased to 65 DEG C, mechanical agitation is allowed to mix for 40 minutes.Again will stirring
Device rotating speed is adjusted to 900r/min, is slowly added dropwise the initiator ammonium persulfate of 0.4% by constant pressure funnel simultaneously, controls
Initiator is added at 30 minutes.Obtain egg white shape white emulsion after reacting 10 hours, pour emulsion into quality
Mark is the Al of 5%2(SO4)3The beaker of solution stirs breakdown of emulsion (wherein Al2(SO4)3The solvent quality of solution
It is equal to the gross mass of this emulsion), repeatedly clean with deionized water and absolute ethyl alcohol the most again, suction filtration, until
Till filtrate not having foam and turbid phenomenon produce, the polymer of i.e. available white；White will be obtained poly-
Compound is placed in vacuum drying chamber and is dried 12 hours at 70 DEG C.Wherein emulsifying agent, deionized water, monomer and draw
The mass percent sum sending out agent is 100%.
(2) at room temperature, with ultrasonic disperser, the nano ceric oxide particle of 0.35% (is equivalent to white
The 5% of look polymer quality) ultrasonic disperse in the DMF of 92.65%, control ultrasonic
Time is 40 minutes, adds the above-mentioned white polymer of 7% afterwards, mechanical agitator is adjusted to 300r/min,
Obtain viscous fluid after continuously stirring 2h at 80 DEG C, then incite somebody to action with the stainless steel scraper posting five layers of tape thickness
To viscous fluid be uniformly coated on polyethylene diagrams two sides, then barrier film is immersed in de-ionized water tank, 4h
After barrier film is removed from water, dry at normal temperatures, proceed in vacuum drying chamber to be dried 36 hours at 52 DEG C,
Thus obtaining lithium ion battery gelatin polymer film, the thickness of this film is 80 μm；Wherein organic solvent, white
The mass percent sum of look polymer and nano ceric oxide particle is 100%.
(3) process by embodiment 1 step (3).
(4) in glove box, with LiMn2O4 as positive electrode active materials, with graphite as negative pole, by gel polymerisation
Thing electrolyte membrance is placed between positive pole and negative pole, is assembled into button cell.
Embodiment 4
(1) at N2Under protective atmosphere protection, the emulsifier sodium lauryl sulfate of 2% is joined 65%
In deionized water, mechanical agitation is allowed to fully dissolve for 40 minutes, adds the monomer methacrylic acid of 32.8%
N-butyl, acrylonitrile and styrene (wherein n-BMA, acrylonitrile and cinnamic mass ratio
For 2:1:1), temperature is increased to 59 DEG C, mechanical agitation is allowed to mix for 40 minutes.Again will stirring
Device rotating speed is adjusted to 700r/min, is slowly added dropwise the initiator sodium peroxydisulfate of 0.2% by constant pressure funnel simultaneously, controls
Initiator is added at 30 minutes.Obtain egg white shape white emulsion after reacting 9 hours, pour emulsion into quality and divide
Number is the Al of 2.5%2(SO4)3The beaker of solution stirs breakdown of emulsion (wherein Al2(SO4)3The solvent quality of solution
It is equal to the gross mass of this emulsion), repeatedly clean with deionized water and absolute ethyl alcohol the most again, suction filtration, until
Till filtrate not having foam and turbid phenomenon produce, the polymer of i.e. available white；White will be obtained poly-
Compound is placed in vacuum drying chamber and is dried 15 hours at 65 DEG C.Wherein emulsifying agent, deionized water, monomer and draw
The mass percent sum sending out agent is 100%.
(2) at room temperature, with ultrasonic disperser, the titanium dioxide nanoparticle of 1.05% (is equivalent to white
The 15% of look polymer quality) ultrasonic disperse in the DMF of 91.95%, control ultrasonic
Time is 40 minutes, adds the above-mentioned white polymer of 7% afterwards, mechanical agitator is adjusted to 300r/min,
Viscous fluid is obtained after continuously stirring 2 hours at 80 DEG C, then with posting the stainless steel scraper of five layers of tape thickness
The viscous fluid obtained is uniformly coated on polyethylene diagrams two sides, then barrier film is immersed in de-ionized water tank,
After 3h, barrier film is removed from water, dry at normal temperatures, proceed to that vacuum drying chamber is dried at 58 DEG C 34 little
Time, thus obtaining lithium ion battery gelatin polymer film, the thickness of this film is 70 μm；Wherein organic solvent,
The mass percent sum of white polymer and titanium dioxide nanoparticle is 100%.
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 5
(1) at N2Under protective atmosphere protection, the emulsifying agent dodecyl sulphate potassium of 2.5% is joined 71%
Deionized water in, mechanical agitation is allowed to fully dissolve for 35 minutes, adds the monomer metering system of 26.25%
Acid N-butyl, acrylonitrile and styrene (wherein n-BMA, acrylonitrile and cinnamic quality
Ratio is 1:1:4), temperature is increased to 63 DEG C, mechanical agitation is allowed to mix for 50 minutes.To stir again
Mix device rotating speed and be adjusted to 810r/min, be slowly added dropwise the initiator potassium persulfate of 0.25% simultaneously by constant pressure funnel, control
System added initiator at 40 minutes.Obtain egg white shape white emulsion after reacting 7 hours, pour emulsion into quality
Mark is the Al of 2.5%2(SO4)3The beaker of solution stirs breakdown of emulsion (wherein Al2(SO4)3The solvent matter of solution
Amount is equal to the gross mass of this emulsion), repeatedly clean with deionized water and absolute ethyl alcohol the most again, suction filtration, directly
Producing to filtrate does not has foam and turbid phenomenon, the polymer of i.e. available white；White will be obtained
Polymer is placed in vacuum drying chamber and is dried 23 hours at 59 DEG C.Wherein emulsifying agent, deionized water, monomer and
The mass percent sum of initiator is 100%.
(2) at room temperature, with ultrasonic disperser, the rare earth particle of 0.50% (is equivalent to white polymer
The 10% of quality) ultrasonic disperse is in the acetone solvent of 94.50%, and controlling ultrasonic time is 40 minutes, afterwards
Add the above-mentioned white polymer of 5%, mechanical agitator is adjusted to 250r/min, continuously stirs at 80 DEG C
Obtain viscous fluid after 2h, then with stainless steel scraper, the viscous fluid obtained be uniformly coated on polypropylene diaphragm two sides,
Then barrier film is immersed in de-ionized water tank, after 3 hours, barrier film is removed from water, dry at normal temperatures,
Proceed to vacuum drying chamber is dried 24 hours at 57 DEG C, thus obtain lithium ion battery gelatin polymer film,
The thickness of this film is 45 μm；The wherein mass percent sum of organic solvent, white polymer and rare earth particle
It is 100%.
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 6
(1) at N2Under protective atmosphere protection, the emulsifier sodium lauryl sulfate of 3.5% is joined 62%
Deionized water in, mechanical agitation is allowed to fully dissolve for 30 minutes, adds the monomer metering system of 34.15%
Acid N-butyl, acrylonitrile and styrene (wherein n-BMA, acrylonitrile and cinnamic quality
Ratio is 4:2:1), temperature is increased to 63 DEG C, mechanical agitation is allowed to mix for 40 minutes.To stir again
Mix device rotating speed and be adjusted to 900r/min, be slowly added dropwise the initiator sodium peroxydisulfate of 0.35% simultaneously by constant pressure funnel, control
Make and add initiator in 40 minutes.Obtain egg white shape white emulsion after reacting 9 hours, pour emulsion into quality and divide
Number is the Al of 3.5%2(SO4)3The beaker of solution stirs breakdown of emulsion (wherein Al2(SO4)3The solvent quality of solution
It is equal to the gross mass of this emulsion), repeatedly clean with deionized water and absolute ethyl alcohol the most again, suction filtration, until
Till filtrate not having foam and turbid phenomenon produce, the polymer of i.e. available white；White will be obtained poly-
Compound is placed in vacuum drying chamber and is dried 30 hours at 55 DEG C.Wherein emulsifying agent, deionized water, monomer and draw
The mass percent sum sending out agent is 100%.
(2) at room temperature, with ultrasonic disperser, the nano-sized iron oxide particle of 0.50% (is equivalent to white
The 10% of polymer quality) ultrasonic disperse is in the oxolane of 94.5%, and controlling ultrasonic time is 40 minutes,
Add the above-mentioned white polymer of 5% afterwards, mechanical agitator is adjusted to 300r/min, stirs the most continuously
Obtain viscous fluid after mixing 2h, then with stainless steel scraper the viscous fluid obtained is uniformly coated on polypropylene-ethylene-
The two sides of propylene sandwich diaphragm, dries at normal temperatures, proceeds to be dried 26 hours at 59 DEG C in vacuum drying chamber,
Thus obtaining lithium ion battery gelatin polymer film, the thickness of this film is 60 μm；Wherein organic solvent, white
The mass percent sum of look polymer and nano-sized iron oxide particle is 100%.
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 7
(1) at N2Under protective atmosphere protection, the emulsifier sodium lauryl sulfate of 3% is joined 69%
In deionized water, mechanical agitation is allowed to fully dissolve for 40 minutes, adds the monomer methacrylic acid of 27.7%
N-butyl, acrylonitrile and styrene (wherein n-BMA, acrylonitrile and cinnamic mass ratio
For 2:2:1), temperature is increased to 57 DEG C, mechanical agitation is allowed to mix for 40 minutes.Again will stirring
Device rotating speed is adjusted to 700r/min, is slowly added dropwise the initiator sodium peroxydisulfate of 0.3% by constant pressure funnel simultaneously, controls
Initiator is added at 30 minutes.Obtain egg white shape white emulsion after reacting 8.5 hours, pour emulsion into quality
Mark is the Al of 3%2(SO4)3The beaker of solution stirs breakdown of emulsion (wherein Al2(SO4)3The solvent quality of solution
It is equal to the gross mass of this emulsion), repeatedly clean with deionized water and absolute ethyl alcohol the most again, suction filtration, until
Till filtrate not having foam and turbid phenomenon produce, the polymer of i.e. available white；White will be obtained poly-
Compound is placed in vacuum drying chamber and is dried 23 hours at 61 DEG C.Wherein emulsifying agent, deionized water, monomer and draw
The mass percent sum sending out agent is 100%.
(2) at room temperature, with ultrasonic disperser, the nanometer lithium metaaluminate particle of 0.50% (is equivalent to white
The 10% of look polymer quality) ultrasonic disperse is in the acetone of 94.5%, and controlling ultrasonic time is 40 minutes,
Add the above-mentioned white polymer of 5% afterwards, mechanical agitator is adjusted to 300r/min, stirs the most continuously
Obtain viscous fluid after mixing 2h, then with stainless steel scraper the viscous fluid obtained is uniformly coated on polypropylene-ethylene-
Propylene sandwich diaphragm two sides, dries at normal temperatures, proceeds to be dried 22 hours at 53 DEG C in vacuum drying chamber,
Thus obtaining lithium ion battery gelatin polymer film, the thickness of this film is 45 μm；Wherein organic solvent, white
The mass percent sum of look polymer and nanometer lithium metaaluminate particle is 100%.
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned reality
Execute the restriction of example, the change made under other any Spirit Essence without departing from the present invention and principle, modification,
Substitute, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (9)
1. the preparation method of a gel polymer electrolyte barrier film, it is characterised in that comprise the steps:
(1) prepare polymer: under inert protective atmosphere is enclosed, by 1～4% emulsifying agent join 60～72%
In ionized water after stirring and dissolving, addition 25～38% monomer methacrylic acid N-butyl, acrylonitrile and styrene,
Temperature is increased to 55～65 DEG C simultaneously；Addition 0.1～0.4% initiator, control to add at 20～50 minutes to draw
Send out agent, after continuously stirring 4～10 hours, obtain egg white shape emulsion；Pouring egg white shape emulsion into mass fraction is 2～5%
Al2(SO4)3Solution stirs breakdown of emulsion, then repeatedly cleans with deionized water and absolute ethyl alcohol, obtain white
Polymer；Again white polymer is vacuum dried；Described percentage is mass percent, wherein emulsifying agent,
The mass percent sum of deionized water, monomer and initiator is 100%；
(2) prepare gelatin polymer film: by nano particle ultrasonic disperse in 89～95% organic solvent in,
Control ultrasonic time be 20～40 minutes, after being uniformly dispersed add 4～10% step (1) prepare white
Polymer, the quality of described nano particle is the 0～20% of white polymer quality, is glued after stirring 1～3h
Magma；The viscous solution obtained is uniformly coated on the two sides of supporter, then is dipped in deionized water initiation
Phase transfer, dries at normal temperatures by the film obtained, vacuum drying, prepares lithium ion battery gel
Polymer film；Described percentage is mass percent, wherein organic solvent, white polymer and nanoparticle
The mass percent sum of son is 100%；
(3) prepare gel polymer electrolyte barrier film: in glove box, by step (2) prepare lithium from
After sub-battery gelatin polymer film soaks 0.5～1 hour in the electrolytic solution, obtain lithium ion battery gel and gather
Polymer electrolyte barrier film.
The preparation method of a kind of gel polymer electrolyte barrier film the most according to claim 1, its feature
Being, in step (1), described emulsifying agent is lauryl sodium sulfate, dodecyl sulphate potassium or dodecane
Base ammonium sulfate；Described monomer methacrylic acid N-butyl, acrylonitrile and cinnamic mass ratio are 1～4:1～2:
1～8；Described initiator is sodium peroxydisulfate, potassium peroxydisulfate or ammonium persulfate.
The preparation method of a kind of gel polymer electrolyte barrier film the most according to claim 1, its feature
Being, in step (2), described organic solvent is in DMF, acetone, oxolane
One or more mixing；Described nano particle is SiO2、Al2O3、SnO2、TiO2、LiAlO2、CeO2、
Fe3O4, rare earth, clay or zeolite；Described supporter be polyethylene film, polypropylene screen, polypropylene-ethylene-
One in propylene sandwich diaphragm.
The preparation method of a kind of gel polymer electrolyte barrier film the most according to claim 1, its feature
Being, the thickness of step (2) described lithium ion battery gel polymer film is 40 μm～80 μm.
The preparation method of a kind of gel polymer electrolyte barrier film the most according to claim 1, its feature
Being, in step (3), described electrolyte is by lithium hexafluoro phosphate, ethylene carbonate, dimethyl carbonate and carbon
Acid methyl ethyl ester composition, wherein the mass ratio of ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate is 1～2:1～2:
1, the molar concentration of lithium hexafluoro phosphate is 0.5～1.5mol/L.
6. a gel polymer electrolyte barrier film, it is characterised in that it is by any one of claim 1 to 5
The preparation method of described a kind of gel polymer electrolyte barrier film prepares.
7. the gel polymer electrolyte barrier film described in claim 6 prepare gel polymer electrolyte lithium from
Application in sub-battery.
Application the most according to claim 7, it is characterised in that described application specifically comprises the following steps that
In glove box, gel polymer electrolyte barrier film is placed between positive pole diaphragm and cathode membrane, can assemble
Become gel polymer electrolyte lithium-ion battery.
Application the most according to claim 8, it is characterised in that the active material of described positive pole diaphragm is
Cobalt acid lithium, LiMn2O4, lithium nickelate, nickel ion doped, nickle cobalt lithium manganate or LiFePO4；Described cathode membrane
Active material be Delanium, native graphite, carbonaceous mesophase spherules, mesophase carbon fiber, soft carbon, hard
Carbon or metal lithium sheet；Described gel polymer electrolyte lithium-ion battery is button cell or soft-package battery.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107565161A (en) * | 2017-08-30 | 2018-01-09 | 华南师范大学 | A kind of gel polymer electrolyte of blended fiber element and preparation method and application |
| CN108878969A (en) * | 2018-06-29 | 2018-11-23 | 华南师范大学 | A kind of fire-retardant gel polymer electrolyte and its preparation and application |
| CN109301319A (en) * | 2018-09-17 | 2019-02-01 | 惠州市典名新能源科技有限公司 | A kind of gel polymer electrolyte and the lithium secondary battery including it |
| CN109830745A (en) * | 2019-01-23 | 2019-05-31 | 广东美尼科技有限公司 | A kind of gel button flexible package lithium cell and preparation process |
| CN112259902A (en) * | 2020-08-28 | 2021-01-22 | 南京理工大学 | Six-arm branched polymeric ionic liquid gel electrolyte diaphragm and preparation method thereof |
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| CN102694203A (en) * | 2012-05-29 | 2012-09-26 | 深圳华粤宝电池有限公司 | Preparation method of gel polymer electrolyte |
| CN104558390A (en) * | 2013-10-12 | 2015-04-29 | 深圳华粤宝电池有限公司 | Polymer for gel polymer electrolyte, preparation method of polymer, gel polymer electrolyte and preparation method of gel polymer electrolyte |
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| CN102694203A (en) * | 2012-05-29 | 2012-09-26 | 深圳华粤宝电池有限公司 | Preparation method of gel polymer electrolyte |
| CN104558390A (en) * | 2013-10-12 | 2015-04-29 | 深圳华粤宝电池有限公司 | Polymer for gel polymer electrolyte, preparation method of polymer, gel polymer electrolyte and preparation method of gel polymer electrolyte |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107565161A (en) * | 2017-08-30 | 2018-01-09 | 华南师范大学 | A kind of gel polymer electrolyte of blended fiber element and preparation method and application |
| CN108878969A (en) * | 2018-06-29 | 2018-11-23 | 华南师范大学 | A kind of fire-retardant gel polymer electrolyte and its preparation and application |
| CN109301319A (en) * | 2018-09-17 | 2019-02-01 | 惠州市典名新能源科技有限公司 | A kind of gel polymer electrolyte and the lithium secondary battery including it |
| CN109301319B (en) * | 2018-09-17 | 2019-07-16 | 惠州市典名新能源科技有限公司 | A kind of gel polymer electrolyte and the lithium secondary battery including it |
| CN109830745A (en) * | 2019-01-23 | 2019-05-31 | 广东美尼科技有限公司 | A kind of gel button flexible package lithium cell and preparation process |
| CN112259902A (en) * | 2020-08-28 | 2021-01-22 | 南京理工大学 | Six-arm branched polymeric ionic liquid gel electrolyte diaphragm and preparation method thereof |
| CN112259902B (en) * | 2020-08-28 | 2022-09-27 | 南京理工大学 | Six-arm branched polymeric ionic liquid gel electrolyte diaphragm and preparation method thereof |
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