CN105958117A - Nano particle doped gel polymer electrolyte, preparation method thereof and application - Google Patents
Nano particle doped gel polymer electrolyte, preparation method thereof and application Download PDFInfo
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- CN105958117A CN105958117A CN201610508747.7A CN201610508747A CN105958117A CN 105958117 A CN105958117 A CN 105958117A CN 201610508747 A CN201610508747 A CN 201610508747A CN 105958117 A CN105958117 A CN 105958117A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of a lithium ion battery, and specifically discloses nano particle doped gel polymer electrolyte, a preparation method thereof and application. According to the preparation method, firstly, through adoption of an emulsion polymerization method, poly-(methyl methacrylate-butyl acrylate-acrylonitrile-styrene) is synthesized according to a certain proportion; then under an ultrasonic condition, the nano particles of certain quantity are evenly dispersed in polymer solution, the polymer solution is stirred to form viscous gel, the gel is coated on two faces of a support and the support is immersed in de-ionized water, thereby triggering phase shift; and finally, drying is carried out, the nano particle doped lithium ion battery gel polymer film is obtained, and the diaphragm is soaked in the electrolyte, thereby obtaining the gel polymer electrolyte is obtained. According to the electrolyte, the preparation method and the application have the advantages of simple production process, short time, high production efficiency, high heat stability, high mechanical strength and high cycle performance; the polymer film has excellent liquid absorption and liquid keeping capacity and has relatively wide temperature use range.
Description
Technical field
The invention belongs to field of lithium ion battery, be specifically related to the gelatin polymer electricity of a kind of doped with nanometer particle
Solve matter and its preparation method and application.
Background technology
Compared with other secondary cells such as Ni-MH battery, nickel-cadmium cell, lead-acid battery, lithium ion battery has
Energy density is high, have extended cycle life, memory-less effect, the advantage such as environmentally friendly, is therefore widely used in
The field such as electronic product, power vehicle.But, current most of commercial Li-ion batteries use liquid to have
Machine electrolyte, due to liquid electrolyte flash-point, steam forces down, mobility by force, therefore easily occurs seepage, exists
Burn the potential safety hazards such as even blast.For solving safety issue, it is proposed that gel polymer electrolyte (GPE),
I.e. use polymeric matrix absorbed electrolyte, the organic bath of flowing is held onto, liquid is converted into solidifying
Colloidal state, reduces the electro-chemical activity of liquid electrolyte.The method is directly effective, and polymer battery chemistry is steady
Qualitative, cycle life is preferable, but it is low to still suffer from room temperature ionic electrical conductivity；The problems such as mechanical strength is the highest.
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 doping
The method for preparing gel polymer electrolyte of nanoparticle.
The present invention, by comparing doping different proportion nanoparticle gel polymerisation physical performance, searches out mechanical strength
Good, heat stability and the optimum doping ratio that chemical stability is excellent, Financial cost is low.
Another object of the present invention is to the gel of the doped with nanometer particle providing a kind of above-mentioned preparation method to prepare
Polymer dielectric.
It is still another object of the present invention to provide the application of the gel polymer electrolyte of above-mentioned doped with nanometer particle.
The object of the invention is achieved through the following technical solutions:
The method for preparing gel polymer electrolyte of a kind of doped with nanometer particle, comprises the following steps:
(1) prepare polymer: under an inert atmosphere, the emulsifying agent of 1～3 mass parts is joined 60～70 matter
After the deionized water of amount part dissolves, add the monomers methyl methacrylate of 27～36.6 mass parts
(MMA), butyl acrylate (BA), acrylonitrile (AN) and styrene (St), stir, simultaneously will reaction
Temperature rises to 55～65 DEG C (can heat up in water-bath or oil bath), controls to add in 20～40 minutes 0.1～0.4
The initiator of mass parts, obtains white emulsion after under agitation carrying out reacting 5～7 hours；White emulsion is fallen
Enter the Al of 2～5 mass parts2(SO4)3Aqueous solution stirs breakdown of emulsion, obtains white precipitate, then use deionized water
Repeatedly clean with dehydrated alcohol, obtain the poly-(methyl methacrylate-butyl acrylate-acrylonitrile of white polymer
-styrene) (being abbreviated as P (MMA-BA-AN-St)), the white polymer vacuum drying that will obtain；
(2) gelatin polymer barrier film is prepared: by organic molten in 89～95 mass parts of nanoparticle ultrasonic disperse
In agent, controlling ultrasonic time is 20～30 minutes；After nanoparticle is uniformly dispersed, add 4～10 mass parts
The white polymer that step (1) prepares, wherein the quality of nanoparticle is white polymer quality
10%～200%, obtain colourless white or flaxen viscous solution after stirring 1～3h at 60～80 DEG C；Will
The viscous solution obtained is uniformly coated on the two sides of supporter, is then dipped in deionized water initiation phase transfer；
After the thin film obtained is dried at normal temperatures, vacuum drying, prepare the lithium-ion electric of doped with nanometer particle
Pond gelatin polymer film；
(3) gel polymer electrolyte barrier film is prepared: by the lithium of the doped with nanometer particle that step (2) prepares
Ion battery gelatin polymer film soaks in the electrolytic solution, after 30～60 minutes, obtains the lithium of doped with nanometer particle
Ion battery gel polymer electrolyte, the gel polymer electrolyte of the most described doped with nanometer particle, above
Operation completes in glove box.
In above-mentioned steps (2), because being not added with any nanoparticle, viscous solution is water white transparency, and nanoparticle
Son itself is white or flaxen, and the amount added is the most, and color is the deepest, so different colours can be obtained
Viscous solution.
In step (1), described inert atmosphere is nitrogen (N2) or argon (Ar) atmosphere；Described emulsifying
Agent is sodium lauryl sulphate, ammonium lauryl sulfate or lauryl sulphate acid potassium；Described monomer metering system
The mass ratio of acid methyl ester (MMA), butyl acrylate (BA), acrylonitrile (AN) and styrene (St) is 2～3:
1～2: 1～4:1～2；Described mixing speed is 800～1000r/min；Described initiator be sodium peroxydisulfate,
Ammonium persulfate. or potassium peroxydisulfate；Described vacuum drying temperature is 50～70 DEG C, and the time is 24～36 hours.
In step (2), described organic solvent is can effectively to dissolve above-mentioned polymer to form homogeneous viscous solution
Organic solvent, but be not limited to one or more in DMF, acetone and oxolane and mix
The organic solvent closed；Described nanoparticle is SiO2、CeO2、Al2O3、SnO2、TiO2、LiAlO2、Fe3O4、
Rare earth, clay or zeolite；Described supporter is polyethylene film, polypropylene screen, polypropylene-ethylene-propylene three layers
One in composite membrane；The thickness of the lithium ion battery gel polymer film of described doped with nanometer particle is
50 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 Ethyl methyl carbonate (EMC) composition, wherein EC:DMC:EMC mass ratio
For 1:1:1, LiPF6Molar concentration be 1mol/L.Described electrolyte is that the triumphant glad battery material of Dongguan City has
The battery function electrolyte that limit company sells.
The gel polymer electrolyte of above-mentioned doped with nanometer particle is preparing gel polymer electrolyte lithium-ion electricity
Application in pond, specifically comprises the following steps that and is put by the gel polymer electrolyte barrier film of above-mentioned doped with nanometer particle
Between positive pole diaphragm and cathode membrane, i.e. it can be assembled into gel polymer electrolyte lithium-ion battery, above
Operation completes in glove box.
The active substance of described positive pole diaphragm is cobalt acid lithium, LiMn2O4, lithium nickelate, nickel ion doped, nickel cobalt manganese
Acid lithium or LiFePO4；The active substance of described cathode membrane is Delanium, native graphite, mesocarbon
Microsphere, 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.
The principle of the present invention is as follows: P (MMA-BA-AN-St) polymer of present invention synthesis has simultaneously
The advantage of monomer MMA, BA, AN and St, then based on this polymer, adds nanoparticle,
The lithium ion battery gel polymer film of doping different proportion nanoparticle it is prepared for phase transfer method.Owing to receiving
Rice corpuscles has quantum size effect, small-size effect and skin effect, to improve polymeric film electrical conductivity,
Mechanical strength and heat stability have certain contribution.Thermal contraction test shows, within the specific limits, along with receiving
The additional proportion of rice corpuscles improves, and the percent thermal shrinkage of polymeric film reduces.This polymeric film is immersed in electrolysis
Forming gel polymer electrolyte in liquid, after being assembled into battery, electro-chemical test shows, this gelatin polymer
Electrolyte electrochemical stable performance, has good ion transmission performance.It is doped with nanoparticle
P (MMA-BA-AN-St) gel electrolyte is ensureing under original stability premise, ionic conductivity and machinery
Intensity has obtained certain raising.Mixed economy cost considers with chemical property, the doping of 100%～150%
Ratio is optimal.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) low cost of raw materials of the present invention, easily obtains, and synthesis technique is simple, and productivity is high, for
Technology produces and provides condition, easily carries out Industry Promotion and utilization.
(2) solvent used by the present invention is deionized water, during phase transfer, be also be immersed in from
Sub-water produces precipitation, does not use volatile organic solvent, environment will not be dropped simultaneously
Low production cost.
(3) polymeric film that the present invention obtains has splendid absorbency and liquid-maintaining capacity, wider temperature
Range.
(4) present invention is doped with nanoparticle, than the P (MMA-BA-AN-St) of the Nano particle that do not adulterates
Polymer dielectric has higher ionic conductivity, mechanical strength and heat stability.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1～5 and the thermogravimetric curve of polymeric film for preparing of reference examples.
Fig. 2 is the embodiment of the present invention 1～5 and the mechanical strength curve of polymeric film for preparing of reference examples.
Fig. 3 is the embodiment of the present invention 1～5 and the percent thermal shrinkage curve of polymeric film for preparing of reference examples.
Fig. 4 is the embodiment of the present invention 1～5 and the following of the gelatin polymer film electrolyte for preparing of reference examples
Ring performance curve.
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.
Embodiment 1
(1) at N2Under protective atmosphere protection, by the emulsifier sodium lauryl sulfate that mass fraction is 1.5 parts
Joining in the deionized water of 68.35 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 2:1:4:1), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.15 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 3 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nano ceric oxide granule of 0.4 mass parts (is equivalent to white polymer matter
The 10% of amount) ultrasonic disperse is in the DMF of 96 mass parts, and controlling ultrasonic time is 40
Minute, it is subsequently adding the above-mentioned white polymer that mass fraction is 4 parts, at 80 DEG C under the conditions of 200r/min,
Continuous stirring obtains faint yellow viscous solution after 2 hours.The viscous solution even spread that will obtain with rustless steel scraper
On polyethylene diagrams two sides, after barrier film is immersed in de-ionized water tank, after 4 hours, barrier film is removed from water,
Dry at normal temperatures, proceed to vacuum drying oven is dried 36 hours at 60 DEG C, thus obtain doped with nanometer particle
Lithium ion battery gel polymer film, the thickness of this film is 70 μm；
(3) in glove box, after above-mentioned lithium ion battery gel polymer film is cut into required size, leaching
Bubble is at electrolyte (1mol/L LiPF6+ EC+DMC+EMC, EC:DMC:EMC mass ratio is 1:1:
1), after 0.5 hour, lithium ion battery gel polymer electrolyte is obtained.
(4) in glove box, with nickel ion doped as positive electrode active materials, with lithium sheet as negative pole, gel is gathered
Polymer electrolyte is placed between positive pole and negative pole, is assembled into button cell.
Embodiment 2
(1) at N2Under protective atmosphere protection, by the emulsifier sodium lauryl sulfate that mass fraction is 1.5 parts
Joining in the deionized water of 68.35 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 2:1:4:1), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.15 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 3 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nano ceric oxide granule of 2 mass parts (is equivalent to white polymer quality
50%) ultrasonic disperse in the DMF of 96 mass parts, control ultrasonic time be 40
Minute, it is subsequently adding the above-mentioned white polymer that mass fraction is 4 parts, at 80 DEG C under the conditions of 200r/min,
Continuous stirring obtains faint yellow viscous solution after 2 hours.The viscous solution even spread that will obtain with rustless steel scraper
On polyethylene diagrams two sides, after barrier film is immersed in de-ionized water tank, after 4 hours, barrier film is removed from water,
Dry at normal temperatures, proceed to vacuum drying oven is dried 36 hours at 60 DEG C, thus obtain doped with nanometer particle
Lithium ion battery gel polymer film, the thickness of this film is 70 μm；
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 3
(1) at N2Under protective atmosphere protection, by the emulsifier sodium lauryl sulfate that mass fraction is 1.5 parts
Joining in the deionized water of 68.35 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 2:1:4:1), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.15 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 3 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nano ceric oxide granule of 4 mass parts (is equivalent to white polymer quality
100%) ultrasonic disperse in the DMF of 96 mass parts, control ultrasonic time be 40
Minute, it is subsequently adding the above-mentioned white polymer that mass fraction is 4 parts, at 80 DEG C under the conditions of 200r/min,
Continuous stirring obtains faint yellow viscous solution after 2 hours.The viscous solution even spread that will obtain with rustless steel scraper
On polyethylene diagrams two sides, after barrier film is immersed in de-ionized water tank, after 4 hours, barrier film is removed from water,
Dry at normal temperatures, proceed to vacuum drying oven is dried 36 hours at 60 DEG C, thus obtain doped with nanometer particle
Lithium ion battery gel polymer film, the thickness of this film is 70 μm；
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 4
(1) at N2Under protective atmosphere protection, by the emulsifier sodium lauryl sulfate that mass fraction is 1.5 parts
Joining in the deionized water of 68.35 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 2:1:4:1), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.15 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 3 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nano ceric oxide granule of 6 mass parts (is equivalent to white polymer quality
150%) ultrasonic disperse in the DMF of 96 mass parts, control ultrasonic time be 40
Minute, it is subsequently adding the above-mentioned white polymer that mass fraction is 4 parts, at 80 DEG C under the conditions of 200r/min,
Continuous stirring obtains faint yellow viscous solution after 2 hours.The viscous solution even spread that will obtain with rustless steel scraper
On polyethylene diagrams two sides, after barrier film is immersed in de-ionized water tank, after 4 hours, barrier film is removed from water,
Dry at normal temperatures, proceed to vacuum drying oven is dried 36 hours at 60 DEG C, thus obtain doped with nanometer particle
Lithium ion battery gel polymer film, the thickness of this film is 70 μm；
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 5
(1) at N2Under protective atmosphere protection, by the emulsifier sodium lauryl sulfate that mass fraction is 1.5 parts
Joining in the deionized water of 68.35 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 2:1:4:1), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.15 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 3 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nano ceric oxide granule of 8 mass parts (is equivalent to white polymer quality
200%) ultrasonic disperse in the DMF of 96 mass parts, control ultrasonic time be 40
Minute, it is subsequently adding the above-mentioned white polymer that mass fraction is 4 parts, at 80 DEG C under the conditions of 200r/min,
Continuous stirring obtains faint yellow viscous solution after 2 hours.The viscous solution even spread that will obtain with rustless steel scraper
On polyethylene diagrams two sides, after barrier film is immersed in de-ionized water tank, after 4 hours, barrier film is removed from water,
Dry at normal temperatures, proceed to vacuum drying oven is dried 36 hours at 60 DEG C, thus obtain doped with nanometer particle
Lithium ion battery gel polymer film, the thickness of this film is 70 μm；
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Reference examples:
Except not adding any nano-particle in step (2), other steps are same as in Example 1.
Test case:
1, thermogravimetric test
Embodiment 1～5 and reference examples in, the polymeric film of the doping different proportion nanoparticle prepared
Thermogravimetric curve is as shown in Figure 1.Thermogravimetric test is to carry out in nitrogen atmosphere, and measurement range is 25 DEG C～800 DEG C,
Heating rate is 10 DEG C of min-1.It will be seen that along with the raising of nanoparticle doped ratio, polymeric film
Thermal decomposition speed is being gradually lowered, and heat decomposition temperature is improving.Wherein, the polymerization obtained in embodiment 5
The heat stability of thing film is the highest, compared with in reference examples without nano-particle polymeric film decomposition temperature improve
About 50 DEG C.The heat stability that polymer is good ensure that lithium ion battery is at charge and discharge process to a certain extent
Use safety.
2, mechanical strength test
By embodiment 1～5 and the polymeric film for preparing of reference examples be cut into the strip of certain specification, draw
Stretching mechanical strength test, the result obtained is as shown in Figure 2.It will be seen that within the specific limits, polymer
The mechanical strength of film improves along with the increase of nanoparticle doped ratio.When the doping ratio of nanoparticle reaches
During to 100%, the mechanical strength of polymeric film reaches 52MPa, and the polymer of any nanoparticle that undopes
Film mechanical strength only has 38MPa.But certain decay is had when doping ratio strengthens further, this should
It is excessive that this is because nanoparticle ratio, and the ratio of polymer reduces relatively, uses DMF
After viscous solution dissolves, viscous solution viscosity reduces, and reduces with the adhesive force of polyethylene film.In general, doping
Nanoparticle plays positive effect to strengthening polymeric film mechanical strength.
3, percent thermal shrinkage test
By embodiment 1～5 and polymeric film heat treatment at 145 DEG C of preparing of reference examples carry out half an hour
Percent thermal shrinkage is tested, and obtains result as shown in Figure 3.It will be seen that along with the increasing of nanoparticle doped ratio
Greatly, the percent thermal shrinkage of polymeric film is being gradually reduced.When doping ratio increases to 200%, polymeric film
Percent thermal shrinkage is reduced to 76% by without 90% during any nano-particle.Lithium ion battery is when discharge and recharge
Certain heat can be produced, if barrier film generation thermal contraction, it is possible to cause positive and negative pole material contact and short-circuit, and
In barrier film, doped with nanometer particle contributes to reducing percent thermal shrinkage, improves the security performance of battery.
4, cycle performance test
By embodiment 1～5 and the lithium ion battery gel polymer electrolyte that obtains of reference examples be assembled into button electricity
Pond, its structure is negative pole (Li)/gel polymer electrolyte/positive pole (LiNi0.5Mn1.5O4), carry out battery and follow
Ring stability test.The condition of button cell test is: room temperature, 0.2C electric current, 3.0～4.9V voltage ranges.
The curve that test obtains is as shown in Figure 4.As seen from the figure, what prepared by the present invention does not has the nanoparticle of interpolation
Gel polymer electrolyte is after circulation 200 weeks, and capability retention is 51%, and adds the reality of nanoparticle
Execute the gel polymer electrolyte that example 2 prepares and have a higher capability retention 73%, case study on implementation 1,3,
4, the capability retention of 5 gel polymer electrolytes prepared is the most all more than 70%.
Embodiment 6
(1) under Ar protective atmosphere is protected, by the emulsifier sodium lauryl sulfate that mass fraction is 1 part
Joining in the deionized water of 68.9 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 2:1:3:2), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.1 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 2 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nanometer silicon dioxide particle of 0.4 mass parts (is equivalent to white polymer
The 10% of quality) ultrasonic disperse is in the DMF of 96 mass parts, and controlling ultrasonic time is
40 minutes, being subsequently adding mass fraction was 4 parts above-mentioned to white polymer, 200r/min bar at 80 DEG C
Under part, continuous stirring obtains thick white liquid after 2 hours.With rustless steel scraper by uniform for the viscous solution obtained
Be coated on polyethylene diagrams two sides, after barrier film is immersed in de-ionized water tank, after 4 hours by barrier film from water
Remove, dry at normal temperatures, proceed to vacuum drying oven is dried 36 hours at 60 DEG C, thus obtain doping and receive
The lithium ion battery gel polymer film of rice corpuscles, the thickness of this film is 50 μm；
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 7
(1) under Ar protective atmosphere is protected, by the emulsifier sodium lauryl sulfate that mass fraction is 1 part
Joining in the deionized water of 68.9 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 2:1:3:1), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.1 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 2 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nanometer silicon dioxide particle of 4 mass parts (is equivalent to white polymer matter
The 100% of amount) ultrasonic disperse is in the DMF of 96 mass parts, and controlling ultrasonic time is
40 minutes, being subsequently adding mass fraction was 4 parts above-mentioned to white polymer, 200r/min bar at 80 DEG C
Under part, continuous stirring obtains thick white liquid after 2 hours.With rustless steel scraper by uniform for the viscous solution obtained
Be coated on polyethylene diagrams two sides, after barrier film is immersed in de-ionized water tank, after 4 hours by barrier film from water
Remove, dry at normal temperatures, proceed to vacuum drying oven is dried 36 hours at 60 DEG C, thus obtain doping and receive
The lithium ion battery gel polymer film of rice corpuscles, the thickness of this film is 50 μm；
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 8
(1) under Ar protective atmosphere is protected, by the emulsifier sodium lauryl sulfate that mass fraction is 2 parts
Joining in the deionized water of 67.8 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 1.5:1:3:2), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.2 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 4 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, (be equivalent to white be polymerized by the nano-aluminium oxide granule of 0.4 mass parts
The 10% of material amount) ultrasonic disperse in the DMF of 96 mass parts, control ultrasonic time
Being 40 minutes, being subsequently adding mass fraction is 4 parts above-mentioned to white polymer, 250r/min at 80 DEG C
Under the conditions of, continuous stirring obtains thick white liquid after 2 hours.With rustless steel scraper by equal for the viscous solution obtained
Even be coated on polyethylene diagrams two sides, after 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 oven to be dried 36 hours at 60 DEG C, thus adulterated
The lithium ion battery gel polymer film of nanoparticle, the thickness of this film is 60 μm；
(3) process by embodiment 1 step (3).
(4) process by embodiment 1 step (4).
Embodiment 9
(1) under Ar protective atmosphere is protected, by the emulsifier sodium lauryl sulfate that mass fraction is 2 parts
Joining in the deionized water of 67.8 mass parts, mechanical agitation is allowed to fully dissolve for 20 minutes, adds 30
The monomers methyl methacrylate (MMA) of mass parts, butyl acrylate (BA), acrylonitrile (AN) and
Styrene (St) (wherein the mass ratio of MMA, BA, AN, St is 3:2:4:1), is increased to 60 DEG C by temperature,
Mechanical agitation is allowed to mix homogeneously in 30 minutes.Again agitator speed is adjusted to 800r/min, leaks by constant voltage simultaneously
Bucket is slowly added dropwise the initiator sodium peroxydisulfate of 0.2 mass parts, adds initiator at 30 minutes.React 8 hours
After obtain white emulsion, emulsion is poured into the Al of 4 mass parts2(SO4)3The beaker of solution stirs breakdown of emulsion, it
After repeatedly clean with deionized water and dehydrated alcohol again, sucking filtration, until filtrate in there is no foam and turbid phenomenon
Till generation, the polymer of i.e. available white；White polymer will be obtained and be placed in vacuum drying oven 60 DEG C
Under be dried 36 hours.
(2) at room temperature, the nano-aluminium oxide granule of 4 mass parts (is equivalent to white polymer
The 100% of quality) ultrasonic disperse in the DMF of 96 mass parts, control ultrasonic time
Being 40 minutes, being subsequently adding mass fraction is 4 parts above-mentioned to white polymer, 250r/min at 80 DEG C
Under the conditions of, continuous stirring obtains thick white liquid after 2 hours.With rustless steel scraper by equal for the viscous solution obtained
Even be coated on polyethylene diagrams two sides, after 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 oven to be dried 36 hours at 60 DEG C, thus adulterated
The lithium ion battery gel polymer film of nanoparticle, the thickness of this film is 60 μm；
(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 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 (10)
1. the method for preparing gel polymer electrolyte of a doped with nanometer particle, it is characterised in that include
Following steps:
(1) prepare polymer: under an inert atmosphere, the emulsifying agent of 1～3 mass parts is joined 60～70 matter
After the deionized water of amount part dissolves, add the monomers methyl methacrylate of 27～36.6 mass parts, propylene
Acid butyl ester, acrylonitrile and styrene, stir, and reaction temperature rises to 55～65 DEG C simultaneously, controls
Add the initiator of 0.1～0.4 mass parts in 20～40 minutes, obtain after under agitation carrying out reacting 5～7 hours
White emulsion；White emulsion is poured into the Al of 2～5 mass parts2(SO4)3Aqueous solution stirs breakdown of emulsion, obtains white
Color precipitates, and then repeatedly cleans with deionized water and dehydrated alcohol, obtains white polymer, white by obtain
Color polymer is in vacuum drying；
(2) gelatin polymer barrier film is prepared: by organic molten in 89～95 mass parts of nanoparticle ultrasonic disperse
In agent；After nanoparticle is uniformly dispersed, add the white polymer that 4～10 mass parts steps (1) prepare,
Wherein the quality of nanoparticle is the 10%～200% of white polymer quality, stirs 1～3h at 60～80 DEG C
After obtain viscous solution；The viscous solution obtained is uniformly coated on the two sides of supporter, be then dipped into from
Sub-water causes phase transfer；The thin film obtained is dried at normal temperatures, vacuum drying, prepare doping and receive
The lithium ion battery gel polymer film of rice corpuscles；
(3) gel polymer electrolyte barrier film is prepared: in glove box, doping step (2) prepared
The lithium ion battery gel polymer film of nanoparticle soaks in the electrolytic solution, after 30～60 minutes, obtains described
The gel polymer electrolyte of doped with nanometer particle.
The preparation side of the gel polymer electrolyte of a kind of doped with nanometer particle the most according to claim 1
Method, it is characterised in that in step (1), described emulsifying agent is sodium lauryl sulphate, lauryl sulphate acid
Ammonium or lauryl sulphate acid potassium；Described initiator is sodium peroxydisulfate, Ammonium persulfate. or potassium peroxydisulfate.
The preparation side of the gel polymer electrolyte of a kind of doped with nanometer particle the most according to claim 1
Method, it is characterised in that described monomers methyl methacrylate, butyl acrylate, acrylonitrile and cinnamic
Mass ratio is 2～3: 1～2: 1～4:1～2.
The preparation side of the gel polymer electrolyte of a kind of doped with nanometer particle the most according to claim 1
Method, it is characterised in that in step (2), described organic solvent be DMF, acetone and
One or more mixing in oxolane；Described nanoparticle is SiO2、CeO2、Al2O3、SnO2、TiO2、
LiAlO2、Fe3O4, rare earth, clay or zeolite；Described supporter be polyethylene film, polypropylene screen, poly-third
One in alkene-ethylene-propylene sandwich diaphragm.
The preparation side of the gel polymer electrolyte of a kind of doped with nanometer particle the most according to claim 1
Method, it is characterised in that the thickness of the lithium ion battery gel polymer film of step (2) described doped with nanometer particle
Degree is 50 μm～80 μm.
The preparation side of the gel polymer electrolyte of a kind of doped with nanometer particle the most according to claim 1
Method, it is characterised in that in step (3), described electrolyte is by lithium hexafluoro phosphate, ethylene carbonate, carbonic acid
Dimethyl ester and Ethyl methyl carbonate composition, wherein ethylene carbonate: dimethyl carbonate: Ethyl methyl carbonate mass ratio
For 1:1:1, the molar concentration of lithium hexafluoro phosphate is 1mol/L.
7. the gel polymer electrolyte of a doped with nanometer particle, it is characterised in that it is by claim 1
Method for preparing gel polymer electrolyte to a kind of doped with nanometer particle described in 6 any one prepares.
8. the gel polymer electrolyte of the doped with nanometer particle described in claim 7 is preparing gelatin polymer
Application in electrolyte lithium-ion battery.
Application the most according to claim 8, it is characterised in that specifically comprising the following steps that of described application
In glove box, the gel polymer electrolyte barrier film of described doped with nanometer particle is placed in positive pole diaphragm and bears
Between the diaphragm of pole, i.e. it can be assembled into gel polymer electrolyte lithium-ion battery.
Application the most according to claim 9, it is characterised in that the active substance of described positive pole diaphragm
For cobalt acid lithium, LiMn2O4, lithium nickelate, nickel ion doped, nickle cobalt lithium manganate or LiFePO4；Described negative electrode film
The active substance of sheet 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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| CN109546205A (en) * | 2018-06-13 | 2019-03-29 | 上海大学 | Using the preparation method of the lithium ion battery of organo-mineral complexing gel polymer electrolyte |
| CN110112009A (en) * | 2019-05-31 | 2019-08-09 | 广州大学 | A kind of capacitor composite electrolyte and its preparation method and application |
| CN111613832A (en) * | 2020-04-21 | 2020-09-01 | 浙江锋锂新能源科技有限公司 | Five-membered monomer copolymerized polymer lithium secondary battery and preparation method thereof |
| CN113680210A (en) * | 2021-08-17 | 2021-11-23 | 安徽智泓净化科技股份有限公司 | Nanofiltration membrane for separating low-valence ions and preparation method thereof |
| CN114512714A (en) * | 2022-01-20 | 2022-05-17 | 贵阳学院 | Composite polymer electrolyte material, preparation method thereof and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109546205A (en) * | 2018-06-13 | 2019-03-29 | 上海大学 | Using the preparation method of the lithium ion battery of organo-mineral complexing gel polymer electrolyte |
| CN110112009A (en) * | 2019-05-31 | 2019-08-09 | 广州大学 | A kind of capacitor composite electrolyte and its preparation method and application |
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| CN113680210A (en) * | 2021-08-17 | 2021-11-23 | 安徽智泓净化科技股份有限公司 | Nanofiltration membrane for separating low-valence ions and preparation method thereof |
| CN114512714A (en) * | 2022-01-20 | 2022-05-17 | 贵阳学院 | Composite polymer electrolyte material, preparation method thereof and lithium ion battery |
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Application publication date: 20160921 |