CN103199301A - Composite gel polymer electrolyte based on solid polymer electrolyte, and preparation method and application thereof - Google Patents
Composite gel polymer electrolyte based on solid polymer electrolyte, and preparation method and application thereof Download PDFInfo
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- CN103199301A CN103199301A CN2013100256757A CN201310025675A CN103199301A CN 103199301 A CN103199301 A CN 103199301A CN 2013100256757 A CN2013100256757 A CN 2013100256757A CN 201310025675 A CN201310025675 A CN 201310025675A CN 103199301 A CN103199301 A CN 103199301A
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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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
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- 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 specifically relates to a composite gel polymer electrolyte and a preparation method and application thereof, belonging to the technical field of lithium ion batteries. The composite gel polymer electrolyte is composed of a composite electrolyte membrane and a liquid electrolyte, wherein the composite electrolyte membrane is composed of two or multiple layers, at least one of the layers is a solid polymer electrolyte capable of transferring lithium ions, and at least another of the layers is a high polymer material different from the solid polymer electrolyte. The composite gel polymer electrolyte provided by the invention has high conductivity, a great lithium ion migration coefficient and good safety performance and can be used for lithium secondary batteries with large capacity, high power and high-energy density.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to class plural gel polymer dielectric and preparation method thereof and application.
Background technology
Lithium secondary battery lithium ion battery especially wherein is as a kind of mechanism of new electrochemical power sources, have advantages such as energy density height, environmental friendliness, memory-less effect, be widely used in since its commercialization in the various portable electric appts such as notebook computer, digital camera, mobile phone, it also is one of desirable energy storage device of mixed power electric car (HEV), plug-in hybrid electric automobile (PHEV), pure electric automobile (EV) and small intelligent electrical network simultaneously.Yet, because LiPF
6The extensive use that is organic electrolyte (to moisture sensitivity, inflammable, easily set off an explosion) makes the fail safe of high capacity lithium ion battery and reliability be under suspicion.In order to solve conventional lithium ion battery security problem, polymer Li-ion battery (Polymer lithium ion batteries) becomes the research focus gradually.The positive and negative electrode material of such battery is identical with conventional lithium ion battery, has just adopted solid polymer to replace organic bath and barrier film.Study maximum polymer and mainly contain following a few class: polyethers (mainly being PEO), polyacrylonitrile (PAN) class, polymethacrylates (PMMA) class and Kynoar (PVDF) class etc.Polymer Li-ion battery has solved traditional lithium ion battery leakage and the big problem of leakage current has easily taken place, and fail safe significantly improves; In addition, polymeric material plasticity is strong, so but such battery has advantages such as thin typeization, arbitrary areaization and arbitrary shapeization, thus can obviously improve the specific capacity of battery.Being used for electrolytical polymer can be pure solid-state (solid polymer electrolyte, solid polymer electrolytes SPEs), also can be the gelinite (gel polymer electrolyte that adds plasticizer, gel polymer electrolytes, GPEs).But the conductivity of solid polymer electrolyte is on the low side (＜10
-4S cm
-1), reach the level of practical application far away; Gel polymer electrolyte has the double properties of solid and liquid electrolyte, and conductivity and liquid organic electrolyte are suitable, and electrochemical window is wideer, and Heat stability is good is subjected to extensive concern.But, gel polymerisation electrolyte bad mechanical strength, the production cost height has limited its application in the large-capacity high-power lithium ion battery greatly; The transport coefficient height of anion, polarization have limited power density or the high current charge-discharge ability of lithium ion battery greatly in the simultaneously general gel polymer electrolyte.
Summary of the invention
The transport coefficient height, the polarization that the objective of the invention is to overcome existing gel polymer electrolyte bad mechanical strength, production cost height, anion are big, extremely difficult shortcoming of in big capacity, high power, high energy density lithium ion battery, being used widely, one class high conductivity, macroion transport number, good mechanical property, security performance height, stable chemical performance, the plural gel polymer dielectric based on solid polymer electrolyte that production cost is low, good with common electrode material matching are provided.
Another object of the present invention is to provide a kind of above-mentioned plural gel method for preparing polymer electrolytes.
An also purpose of the present invention is to provide a kind of application of above-mentioned plural gel polymer dielectric, namely is used for lithium secondary battery.
A class plural gel polymer dielectric provided by the invention, described plural gel polymer dielectric is made up of composite electrolyte membrane and liquid electrolyte, wherein composite electrolyte membrane is made up of two-layer or multilayer, wherein having one deck at least is solid polymer electrolyte, and having one deck at least is the macromolecular material different with this solid polymer electrolyte.
Above-mentioned solid polymer electrolyte is for transmitting the polymer of lithium ion, macromolecular material beyond this above-mentioned solid polymer electrolyte not only comprises the solid polymer electrolyte different with this solid polymer electrolyte, also comprise polyolefin, polyamide, polyimides, poly-aramid fiber, polyarylether, polyester, the copolymer, the blend that also comprise simultaneously them also can add suitable inorganic filler simultaneously in these polymer.
Above-mentioned polyolefin comprises polyethylene, polypropylene, Kynoar, poly-(biasfluoroethylene-hexafluoropropylene), above-mentioned polyester comprises poly-(ethylene glycol-terephthalate), and above-mentioned inorganic filler comprises aluminium oxide, silica, titanium oxide, zirconia, aLi
2O-bAl
2O
3-cTiO
2-dP
2O
5The mixture of the compound that (a, b, c, d are between 1-100) forms, imvite, molecular sieve or they both or multiple compound.
Above-mentioned liquid electrolyte includes the solution of organic compounds or ionic liquid and lithium salts.
The invention provides the plural gel method for preparing polymer electrolytes, its concrete steps are:
(1) at first adopt solwution method or heating mixing method to prepare solid polymer electrolyte membrane;
(2) adopt solwution method, heating mixing method, infusion method, casting method or electrospinning method then, will be compound with above-mentioned solid polymer electrolyte macromolecular material and above-mentioned solid polymer electrolyte membrane in addition, form the structure of composite membrane of two-layer or multilayer;
(3) above-mentioned composite membrane is placed vacuum drying chamber, the heating, vacuum drying is removed possible trace solvent;
(4) in the anhydrous and oxygen-free environment, above-mentioned dried composite membrane is immersed in the electrolyte 1 minute to 48 hours, obtains the plural gel polymer dielectric.
The thickness of the solid polymer electrolyte membrane described in the above-mentioned steps (1) is the 1-30 micron;
One deck is above-mentioned solid polymer electrolyte membrane in the described two-layer structure of composite membrane of above-mentioned steps (2), and one deck is the polymer material film beyond this solid polymer electrolyte in addition; In the described MULTILAYER COMPOSITE membrane structure, one deck being arranged in the middle of at least is above-mentioned solid polymer electrolyte membrane, and having one deck at least is polymer material film beyond this solid polymer electrolyte; The thickness of described composite membrane is the 5-50 micron.
The preparation of the described plural gel polymer dielectric of above-mentioned steps (4) can be carried out in glove box, is argon atmospher in the glove box, and moisture is less than 1ppm.
The described electrolyte of above-mentioned steps (4) can be made of lithium hexafluoro phosphate and carbonates solvent, and the molar concentration of lithium hexafluoro phosphate is between 0.5 M-2 M.
The invention provides a kind of application of above-mentioned plural gel polymer dielectric, namely be used for lithium secondary battery.
The present invention adopts the plural gel polymer dielectric not only to have the characteristics that the solid polymer electrolyte mechanical strength is big, production cost is low, and the conductivity height, electrochemical window is wide, good cycle, the security performance height can be used for the lithium secondary battery of big capacity, high power, high-energy-density.
Description of drawings
Fig. 1 (a) is the molecular structural formula of embodiment 2 gained solid polymer electrolytes;
Fig. 1 (b) is the molecular structural formula of embodiment 3 gained solid polymer electrolytes;
The charging and discharging curve of Fig. 2 embodiment 7 and cycle performance;
The charging and discharging curve of Fig. 3 embodiment 8 and cycle performance;
Fig. 4 is charging and discharging curve and the cycle performance figure of Comparative Examples 2 of the present invention.
Embodiment
(1) with polyethylene glycol oxide (molecular weight 100,000), LiClO
4, TiO
2(particle diameter 50 nanometers) carry out weighing for the ratio of 8.7:1:0.3 by mass percentage, under agitation be heated to 120 ℃, become uniform solid solution, be poured into then on the corrosion resistant plate, being pressed into thickness is 10 microns solid polymer electrolyte membrane, and is chilled to room temperature.
(2) under molten condition, be 10 microns porous polyethylene membranes by the thickness that obtains 80 ℃ of hot-stretch, then this polyethylene film is placed above-mentioned solid polymer electrolyte membrane above, be heated to 60 ℃ then, compacting is 1 hour under 10 atmospheric pressure, obtains the solid polymer electrolyte composite membrane.
(3) above-mentioned composite membrane is cut into suitable size after, place the dry traces of moisture of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature, shifts glove box anhydrous, anaerobic.Then the solid polymer electrolyte composite membrane is immersed in 1 M LiPF
6Namely got the plural gel polymer dielectric in the electrolyte (LB315 is available from Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City) in 6 hours.
The test of plural gel polymer dielectric performance:
The pick up (h) of the PEO/PVDF solid polymer electrolyte composite membrane that above-described embodiment 1 is obtained adopts following formula (1) to calculate:
η= (W
t – W
0) / W
0 × 100% (1)
W wherein
0And W
tBe respectively composite membrane and inhale 1 M LiPF
6Weight before and after the electrolyte (LIB315, Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City).
With composite membrane with 1 M LiPF
6After electrolyte (LIB315) is saturated, the temperature when adopting differential scanning method (DSC, instrument are Perkin-Elmer TGA7/DSC7) measurement electrolyte all to volatilize.
PEO/PVDF plural gel polymer dielectric that above-described embodiment 1 is obtained has carried out the test of conductivity, transference number of ions.Conductivity adopts AC impedence method (CHI660C, Shanghai occasion China company), and frequency range is 10 Hz-100 kHz, two stainless steels very wherein, and the centre is the plural gel polymer dielectric, and its area is greater than stainless steel, and conductivity is calculated by formula (2):
σ = l / (R b A) (S cm
-1)
(2)
Wherein,
σBe conductivity,
R b Be the impedance of film,
lBe the thickness of film,
AIt is the pole piece area.
Lithium ion transference number adopts the test of timing coulometry, two lithium sheets very wherein, and the centre is the plural gel polymer dielectric, and voltage is 10mV, and its size is calculated by formula (3):
t
Li + = I
ss/ I
0 (3)
Wherein, I
SsBe the resulting steady-state current value of timing coulometry, I
0It is the resulting initial state current value of timing coulometry.
Measured the results are summarized in the table 1.
(1) polyvinyl alcohol (PVA, alcoholysis degree 〉=98%, Mw:105000,200 mg) and boric acid (148 mg) are dissolved among the 20 ml dimethyl sulfoxide (DMSO) DMSO, 80 ℃ of heating 8 hours, obtain transparent solution then.Then add 88 mg Li
2CO
3With 300 mg oxalic acid, be heated to 100 ℃ of reactions 24 hours, cool to room temperature.Solution casting to glass plate, is dried in 70 ℃ of baking ovens, and desolventizing obtains thickness and is 30 μ m poly-(vinyl alcohol-boric acid-lithium oxalate), and its structural representation is in Fig. 1 a, the structure similar of ionic conduction group and LiBOB.
(2) under molten condition, be 10 microns porous polypropylene films by the thickness that obtains 100 ℃ of hot-stretch, then this polypropylene screen is placed the top of above-mentioned solid-state poly-lithium borate film and below, be heated to 70 ℃ then, compacting is 2 hours under 10 atmospheric pressure, obtains the solid polymer electrolyte composite membrane.
(3) above-mentioned composite membrane is cut into suitable size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature, shifts glove box anhydrous, anaerobic.Then the solid polymer electrolyte composite membrane is immersed in 1 M LiN (CF
3SO
2)
2Namely got the plural gel polymer dielectric in the electrolyte (solvent is the mixture of vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 1:1:1) in 40 hours.
The performance test of gained plural gel polymer dielectric film is with embodiment 1, the results are summarized in the table 1 of gained.
Embodiment 3
(1) polyacrylic acid (PAA, Mw:450000,200 g), boric acid (148 g), 20 ml deionized waters are heated to 80 ℃, obtain transparent solution.Then add 59g LiOH and 300 g oxalic acid, be heated to 100 ℃ of reactions 24 hours, cool to room temperature.Solution casting to glass plate, is dried in 70 ℃ of baking ovens, and desolventizing obtains thickness and is 30 μ m poly-(acrylic acid-boric acid-lithium oxalate), and its structural representation is in Fig. 1 b, the structure similar of ionic conduction group and LiBOB.
(2) be that 10% ratio is dissolved in the N-N-methyl-2-2-pyrrolidone N-by mass percentage with P (VDF-HFP), then with this solution casting poly-(acrylic acid-boric acid-lithium oxalate) film surface at above-mentioned (1) gained, be heated to 100 ℃ then, carry out vacuumize, obtain the solid polymer electrolyte composite membrane.
(3) above-mentioned composite membrane is cut into suitable size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature, shifts glove box anhydrous, anaerobic.Then the solid polymer electrolyte composite membrane is immersed in the 0.8 M LiBOB electrolyte (solvent is the mixture of vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 1:1:1) 40 hours and namely gets the plural gel polymer dielectric.
The performance test of gained plural gel polymer dielectric film is with embodiment 1, the results are summarized in the table 1 of gained.
Embodiment 4
(1) be that the mixture of 1:9 joins in N-N-methyl-2-2-pyrrolidone N-(100 ml) solvent with Lithium polyacrylate (1g) and polymethyl methacrylate (9g) mass ratio, be heated to 60 ℃ of dissolvings, add 0.2g silica (average grain diameter 100 nanometers) then, then mixed liquor is poured on the glass plate, in 70 ℃ of baking ovens, dry, desolventizing, obtaining thickness is Lithium polyacrylate-polymethyl methacrylate dielectric film of 15 μ m.
(2) be that 10% ratio is dissolved in the N-N-methyl-2-2-pyrrolidone N-by mass percentage with PVDF, then this solution carried out electrospinning under the high pressure of 30KV, be heated to 80 ℃ then, carry out vacuumize, obtain thickness and be 5 microns pvdf membrane; With above-mentioned (1) gained Lithium polyacrylate-the polymethyl methacrylate dielectric film is as the intermediate layer, the electrospinning pvdf membrane is two-layer as the outside, obtains the composite membrane of " sandwich " structure then.
(3) above-mentioned composite membrane is cut into suitable size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature, shifts glove box anhydrous, anaerobic.Then the solid polymer electrolyte composite membrane is immersed in the 0.8 M LiBOB electrolyte (solvent is the mixture of vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 1:1:1) 40 hours and namely gets the plural gel polymer dielectric.
The performance test of gained plural gel polymer dielectric film is with embodiment 1, the results are summarized in the table 1 of gained.
(1) PPOX (molecular weight 200,000), LiBOB are carried out weighing for the ratio of 9:1 by mass percentage, under agitation be heated to 130 ℃, become uniform solid solution, be poured on the corrosion resistant plate then, being pressed into thickness is 15 microns solid polymer electrolyte membrane, and is chilled to room temperature.
(2) be that (model 117 0.1kg) is soaked and stagnated in LiOH saturated solution (2kg), and 48 spend deionised water, drying after little, obtain the Nafion film of lithiumation for 20 microns Nafion film with thickness; Then with the solid polymer dielectric film of above-mentioned (1) gained under 70 ℃, be compressed on the Nafion film of lithiumation under the atmospheric pressure of 20MPa, obtain composite membrane.
(3) above-mentioned composite membrane is cut into suitable size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature, shifts glove box anhydrous, anaerobic.Then the solid polymer electrolyte composite membrane is immersed in the ionic liquid of 0.8 M LiBOB in (ionic liquid consists of 1-alkyl-2,3-methylimidazole trifluoromethyl sulfonic acid) 30 hours and namely gets the plural gel polymer dielectric.
The performance test of gained plural gel polymer dielectric film is with embodiment 1, the results are summarized in the table 1 of gained.
Embodiment 6
(1) with concentration be the polyacrylonitrile (molecular weight 150,000) of 8wt.% at N, N '-dimethyl formamide solution is coated on the corrosion resistant plate, 80 ℃ of dry backs, cooling make thickness and are 15 microns solid polymer electrolyte membrane.
(2) with poly-(ethylene glycol-terephthalate) (Mw:600,000) of fusion 140 ℃ by fusion drawn, obtaining thickness and be 40 microns, average pore size is that 100nm, porosity are poly-(ethylene glycol-terephthalate) film of 50%; Then the solid polymer dielectric film of above-mentioned (1) gained is compressed on poly-(ethylene glycol-terephthalate) above the film under 70 ℃, under the atmospheric pressure of 20MPa, obtains composite membrane.
(3) above-mentioned composite membrane is cut into suitable size after, place the dry trace solvent of removing of following 24 hours of 80 ℃ of conditions of vacuum drying chamber, vacuum is chilled to room temperature, shifts glove box anhydrous, anaerobic.Then the solid polymer electrolyte composite membrane is immersed in 0.6 MLiPF
6With namely got the plural gel polymer dielectric in (solvent is the mixture of vinyl carbonate, formic acid dimethyl ester, formic acid diethylester volume ratio 2:1:1) in the mixed solution of 0.4 M LiBOB in 5 hours.
The performance test of gained plural gel polymer dielectric film is with embodiment 1, the results are summarized in the table 1 of gained.
Comparative Examples 1
With the commercial li-ion battery diaphragm (Celgard 2730, PE) be cut into appropriate size after, placed under 80 ℃ of conditions of vacuum drying chamber drying under reduced pressure 24 hours, vacuum is chilled to room temperature and shifts into glove box.Carry out needing Celgard 2730 barrier films are immersed in 1 mol l before the electro-chemical test
-1LiPF
6In the electrolyte (model LIB315 is available from Guotai Huarong Chemical New Material Co., Ltd., Zhangjiagang City) 6 hours.
The performance test of gained barrier film is with embodiment 1, the results are summarized in the table 1 of gained.
The electrochemical property test result of table 1 embodiment 1-6 and Comparative Examples 1
Embodiment 7
With the plural gel polymer dielectric of embodiment 2 gained as electrolyte and barrier film, with LiFePO
4, conductive black, adhesive PVDF (mass ratio 9:0.4:0.6) mixture as positive pole, as negative pole, form lithium ion battery with the mixture of graphite, conductive black, adhesive PVDF (mass ratio 9.2:0.3:0.5).Discharge and recharge experiment between the 2.5-4.2V then under 0.2C, the charging of gained, discharge curve and cycle performance are illustrated in Fig. 2.
Embodiment 8
With the plural gel polymer dielectric of embodiment 3 gained as electrolyte and barrier film, with LiFePO
4, conductive black, adhesive PVDF (mass ratio 9:0.4:0.6) mixture as positive pole, as negative pole, form lithium ion battery with the mixture of graphite, conductive black, adhesive PVDF (mass ratio 9.2:0.3:0.5).Discharge and recharge experiment between the 2.5-4.2V then under 0.2C, the charging of gained, discharge curve and cycle performance are illustrated in Fig. 3.
Comparative Examples 2
(Celgard 2730, PE) as barrier film, as electrolyte, as negative pole, form lithium ion battery with the mixture of graphite, conductive black, adhesive PVDF (mass ratio 9.2:0.3:0.5) with LIB315 with the commercial li-ion battery diaphragm.Discharge and recharge experiment between the 2.5-4.2V then under 0.2C, the charging of gained, discharge curve and cycle performance are illustrated in Fig. 4.
The result of embodiment 1-6 and Comparative Examples 1 is to recently from table 1, have high ionic conductivity, high lithium ion transport coefficient based on the lithium ion battery gel polymer electrolyte of solid polymer electrolyte material, and the temperature that electrolyte volatilizees fully is all greater than 140 ℃, be higher than 65 ℃ of Comparative Examples far away, have very excellent safety energy.
From embodiment 7,8 and the result (Fig. 2, Fig. 3 and Fig. 4) of Comparative Examples 2 to recently, adopt the lithium secondary battery of plural gel polymer dielectric, in charge and discharge process, has less polarization, and the capacity maintenance is stable, and lithium ion battery that this explanation plural gel polymer dielectric is assembled into has higher energy efficiency.
The situation of comprehensive above-mentioned Comparative Examples and embodiment shows that the plural gel polymer dielectric has good attraction for the lithium secondary battery of high safety performance.
Claims (20)
1. plural gel polymer dielectric, it is characterized in that described plural gel polymer dielectric is made up of composite electrolyte membrane and liquid electrolyte, wherein composite electrolyte membrane is made up of two-layer or multilayer, wherein having one deck at least is solid polymer electrolyte, and having one deck at least is the macromolecular material different with this solid polymer electrolyte.
2. plural gel polymer dielectric as claimed in claim 1 is characterized in that described solid polymer electrolyte is for transmitting the polymer of lithium ion.
3. plural gel polymer dielectric as claimed in claim 2, it is characterized in that the described polymer that can transmit lithium ion comprises polyethylene glycol oxide (PEO), PPOX (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), poly-borate or poly-boric acid lithium salts, poly-aluminic acid ester or poly-aluminic acid ester lithium salts, polysiloxanes, poly-phosphine piperazine, side chain has the polymer of carboxylic acid lithium, side chain has the polymer of sulfonic acid lithium, perhaps their copolymer, blend is formed, and also can add the low lithium salts of molecular weight and inorganic filler in these polymer simultaneously.
4. plural gel polymer dielectric as claimed in claim 3 is characterized in that described poly-boric acid lithium salts is polyacrylic acid, boric acid, oxalic acid and Li
2CO
3Perhaps LiOH reacts resulting polymers or polyvinyl alcohol, boric acid, oxalic acid and Li
2CO
3Perhaps LiOH reacts resulting polymers.
5. plural gel polymer dielectric as claimed in claim 3 is characterized in that the polymer that described side chain has a carboxylic acid lithium is Lithium polyacrylate.
6. plural gel polymer dielectric as claimed in claim 3 is characterized in that the polymer that described side chain has a sulfonic acid lithium is the lithium salts of Nafion film.
7. as any described plural gel polymer dielectric among the claim 3-6, it is characterized in that the low lithium salts of described molecular weight is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, LiBOB (di-oxalate lithium borate), LiDFBO (difluorine oxalic acid boracic acid lithium), LiCF
3SO
3, LiN (CF
3SO
2)
2, LiN (RfOSO
2)
2, LiC (SO
2CF
3)
3Perhaps they both or the mixture of multiple lithium salts.
8. as any described plural gel polymer dielectric among the claim 3-6, it is characterized in that described inorganic filler comprises aluminium oxide, silica, titanium oxide, zirconia, aLi
2O-bAl
2O
3-cTiO
2-dP
2O
5The mixture of the compound that (a, b, c, d are between 1-100) forms, imvite, molecular sieve or they both or multiple compound.
9. as any described plural gel polymer dielectric among the claim 1-8, it is characterized in that the macromolecular material beyond described this solid polymer electrolyte not only comprises the solid polymer electrolyte different with this solid polymer electrolyte, also comprise polyolefin, polyamide, polyimides, poly-aramid fiber, polyarylether, polyester, also comprise simultaneously their copolymer, blend, also can add suitable inorganic filler.
10. plural gel polymer dielectric as claimed in claim 9 is characterized in that described polyolefin comprises polyethylene, polypropylene, Kynoar, poly-(biasfluoroethylene-hexafluoropropylene).
11. plural gel polymer dielectric as claimed in claim 9 is characterized in that described polyester comprises poly-(ethylene glycol-terephthalate).
12. as any described plural gel polymer dielectric among the claim 1-11, it is characterized in that described liquid electrolyte includes the solution of organic compounds or ionic liquid and lithium salts.
13. one kind as any described plural gel method for preparing polymer electrolytes among the claim 1-12, it is characterized in that concrete steps are:
(1) at first adopt solwution method or heating mixing method to prepare solid polymer electrolyte membrane;
(2) adopt solwution method, heating mixing method, infusion method, casting method or electrospinning method then, will be compound with above-mentioned solid polymer electrolyte macromolecular material and above-mentioned solid polymer electrolyte membrane in addition, form the structure of composite membrane of two-layer or multilayer;
(3) above-mentioned composite membrane is placed vacuum drying chamber, the heating, vacuum drying is removed possible trace solvent;
(4) in the anhydrous and oxygen-free environment, above-mentioned dried composite membrane is immersed in the liquid electrolyte 1 minute to 48 hours, obtains lithium ion battery gel polymer electrolyte.
14. method as claimed in claim 13, the thickness that it is characterized in that the solid polymer electrolyte membrane described in the step (1) is the 1-30 micron.
15. as any described method in the claim 13,14, it is characterized in that one deck is above-mentioned solid polymer electrolyte membrane in the described two-layer structure of composite membrane of step (2), one deck is the polymer material film beyond this solid polymer electrolyte in addition.
16. as any described method in the claim 13,14, it is characterized in that in the structure of composite membrane of the described multilayer of step (2), at least in the middle of one deck being arranged is above-mentioned solid polymer electrolyte membrane, and having one deck at least is this solid polymer electrolyte polymer material film in addition.
17. as any described method among the claim 13-16, the thickness that it is characterized in that the composite membrane described in the step (2) is the 5-60 micron.
18. as any described method among the claim 13-17, it is characterized in that the described anhydrous and oxygen-free environment of step (4) is glove box, be argon gas atmosphere in the glove box, moisture is less than 1ppm.
19. as any described method among the claim 13-17, it is characterized in that the described liquid electrolyte of step (4) includes the solution of organic compounds or ionic liquid and lithium salts.
20. application as plural gel polymer dielectric as described among the claim 1-19 any, this is applied as a kind of electrolyte of secondary cell and barrier film, the negative pole of this secondary cell is the alloy of alloy, silicon or silicon of alloy, material with carbon element, tin, the tin of lithium metal, lithium metal, just very Li M ' O
2(M '=a kind of among Co, Ni, Mn, the Co, two kinds of elements or two or more element) or Li M ' PO
4(M '=a kind of among Fe, Mn, the Co, two kinds or 2 kinds of elements and more than).
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105118947A (en) * | 2015-09-13 | 2015-12-02 | 中南大学 | Method for preparing lithium ion battery diaphragm |
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