CN103804892B - A kind of polymer porous film and preparation method thereof and the application in gel polymer electrolyte - Google Patents
A kind of polymer porous film and preparation method thereof and the application in gel polymer electrolyte Download PDFInfo
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- CN103804892B CN103804892B CN201310231733.1A CN201310231733A CN103804892B CN 103804892 B CN103804892 B CN 103804892B CN 201310231733 A CN201310231733 A CN 201310231733A CN 103804892 B CN103804892 B CN 103804892B
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- porous film
- polymer porous
- electrolyte
- polymer
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 51
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- 239000003792 electrolyte Substances 0.000 claims abstract description 37
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- 238000001879 gelation Methods 0.000 claims abstract description 10
- 230000008961 swelling Effects 0.000 claims abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims description 39
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- 239000002904 solvent Substances 0.000 claims description 18
- 239000000693 micelle Substances 0.000 claims description 17
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- 238000010382 chemical cross-linking Methods 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
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- 229910012464 LiTaF6 Inorganic materials 0.000 claims description 3
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
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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
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Abstract
The present invention provides a kind of polymer porous film and preparation method thereof that the Pioloform, polyvinyl acetal polymer handled using polyurethane-reinforcement is obtained, the perforated membrane is uniform-distribution with interconnected pore, with preferable absorption electrolyte ability, imbibition rate is up to 300% or more, the gelation of system is realized by absorption swelling electrolyte, and perforated membrane and gel rubber system can exist steadily in the long term.This kind of gel polymer electrolyte close to liquid electrolyte conductivity average value 1.0 × 10‐3S/cm, electrochemical stability window 2.0V~5.0V, mechanical performance and significantly improve with the compatibility of electrode, can be used as gel polymer electrolyte application, improve battery security.Simultaneously, it is no longer necessary to using the diaphragm in liquid electrolyte systems or other battery systems as support.
Description
Technical field
The invention belongs to thin polymer film preparation and application technical field, in particular to a kind of polymer porous film and its system
Preparation Method, and absorption are swollen application of the stabilising system of electrolyte as gel polymer electrolyte.
Background technique
Gelatin polymer is widely used, the gel polymer electrolyte body as substitution lithium ion battery liquid electrolyte
System, has the relatively high ionic conductivity close to liquid electrolyte, but also with the without leakage feature of solid electrolyte.It can solve
Certainly organic electrolyte has high volatility and combustibility, is likely to occur the safety such as rupture, on fire and explosion in a short-circuit situation
Problem.Being large-scale lithium ion battery, applying in new-energy automobile field, solar energy, wind power generation energy storage device provides guarantor
Barrier.
Studying at present more mainly has polyethylene glycol oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate
(PMMA), the polymer containing polar group such as Kynoar (PVDF) is the gel polymer electrolyte of matrix.
PEO base gel polymer electrolyte easily crystallizes, and causes room-temperature conductivity low；In PAN base gel polymer electrolyte
Gelatin polymer film and lithium electrode interface passivation phenomenon are serious, and in the case that plasticizer loading is high, mechanical performance decline is more serious；
PMMA base gel polymer electrolyte mechanical performance is poor；Polymer architecture is regular in PVDF base gel polymer electrolyte, easily
Crystallization, is unfavorable for ionic conduction.
It can be seen that the common generally existing problem of gelatin polymer base, gel membrane stability, mechanical performance and compatible with electrode
Property still needs to improve.In addition, there are no properly settle for the problem of oozing out electrolyte from gel.
Summary of the invention
Pioloform, polyvinyl acetal and its derivative have that film forming, heat resistance, water resistance are good, chemical structure is relatively stable etc.
Advantage, early has been supplied in the fields such as adhesive, chemical coating, medical sthptic sponge and is widely used, and also has a small amount of researcher will
It is used in lithium ion battery gel polymer electrolyte system.It mainly contains following several structural units (wherein R=H, first
Base, ethyl or propyl):
Interior field, which is controlled etc., is prepared for a kind of gel polymer electrolyte in patent of invention [CN101176233A], by poly- second
Enol acetal or derivatives thereof, solvent, lithium hexafluoro phosphate composition.Lithium hexafluoro phosphate plays certain catalytic action, makes polyvinyl alcohol
Acetal or derivatives thereof further polymerize, and forms polymer dielectric, inhibits the leakage of electrolyte, while discharge performance is changed
It is kind.
Bamboo field good fortune history etc. is mentioned in patent of invention [CN101288198A], by adjusting cyclic compound in organic solvent
With the composition ratio of linear compounds, the dissolubility and ionic conductivity of Pioloform, polyvinyl acetal are improved.
The former clear male of Chinese juniper etc. mentions in patent of invention [CN101103070A], reduces polyvinyl alcohol by the modified method of acid
The ratio of vinyl alcohol units in acetal implements acid modification and the Intramolecular exchange of acetal ring is not only caused to react, but also isolated second
Alcohol units become the structure of multiple connections, thus improve the gelatinization performance of organic solvent.
It can be seen that Pioloform, polyvinyl acetal based polyalcohol has the good prospect applied on lithium ion battery gel polymer, but poly-
Dissolubility is high in the organic solvents such as carbonic ester for vinyl acetal and its derivative, cannot be stabilized, therefore above-mentioned gel is poly-
When polymer electrolyte prepares jelly glue polymer battery by polymerized in-situ technique, it is necessary to place diaphragm element, interface is caused to increase
It is more.
Li Fang magnitude is prepared for a kind of cross-linking polyvinyl alcohol contracting of soluble reticularly in patent of invention [CN1800234A]
Aldehyde polyurethane, wherein use dibutyl tin dilaurate or tin dilaurate as catalyst, it is different using 4,4 '-diphenyl methanes two
Polyvinyl acetal is cross-linked into reticular structure by cyanate (MDI), this kind of polyurethane-reinforcement solid powder can dissolve, for applying
The purposes such as material, paint, binder.
At present there is not yet preparing Pioloform, polyvinyl acetal base using invention method in the article and patent delivered
Perforated membrane, and make report of its gelation as polymer dielectric.
The purpose that the present invention utilizes is, provides a kind of Pioloform, polyvinyl acetal and its derivative perforated membrane and its preparation side
Method, the perforated membrane is by chemical crosslinking at three-dimensional netted rock-steady structure.Above-mentioned polymer porous film has played polyvinyl alcohol contracting
The advantages that excellent film forming that aldehyde and its derivative have, heat resistance, good water resistance, metastable chemical structure,
Above-mentioned polymer porous film and preparation method thereof solves the organic in carbonic ester etc. of Pioloform, polyvinyl acetal and its derivative simultaneously
Dissolubility is high in solvent, the problem of cannot being stabilized, and chemical stability significantly improves.Above-mentioned polymer porous film has preferable
Absorption electrolyte ability, imbibition rate is up to 300% or more, by absorption swelling electrolyte (including the electrolysis based on carbonic ester
Plastidome) gelation of system is realized, and also perforated membrane and gel rubber system can exist steadily in the long term.
It is further an object that above-mentioned polymer porous film is applied in gel polymer electrolyte, especially
It is to be applied in gel polymer lithium ion battery.Due to above-mentioned polymer porous film and the gel polymer electrolyte of formation
Can exist steadily in the long term, be not in the problem of dissolution and electrolyte of the polymer porous film in system are oozed out, it is above-mentioned
Polymer porous film will be integrally formed in electrolyte swell gel or initiation polymerized in-situ with electrolyte, not needed using liquid
Diaphragm in body electrolyte system or other battery systems avoids interface and increases as support, can effectively improve gel
The ionic conductivity of polymer dielectric.Also, due to the polymer porous film by absorption swelling electrolyte (including with carbonic acid
Electrolyte system based on ester) gelation that realizes system has when being applied in gel polymer electrolyte
The without leakage feature of solid electrolyte；Simultaneously as transmission speed of the ion in gel polymer electrolyte is greater than in solid-state
Transmission speed in electrolyte when the polymer porous film is applied in gel polymer electrolyte, can be obtained relative to solid
The higher conductivity of state electrolyte.And for liquid electrolyte, which is applied to gelatin polymer electricity
Leakage existing for liquid electrolyte will not be led to the problem of when Xie Zhizhong, while can obtain the electricity of substantially equal with liquid electrolyte
Conductance, and the polymer porous film is applied to gel polymer electrolyte and can be convenient battery assembly.In addition, traditionally, gathering
Vinyl acetal and its derivative are used as binder, have good adhesive property.Polymer porous film hair according to the present invention
The bonds well performance of Pioloform, polyvinyl acetal and its derivative has been waved, it is therefore, above-mentioned poly- compared to other polymer porous films
Closing the gel polymer electrolyte that object perforated membrane is formed has the binding force and compatibility excellent with electrode, reduces interface electrification
Polarization is learned, electrochemical stability is high, average value 10 of the conductivity close to liquid electrolyte conductivity‐3S/cm.And have high
Mechanical performance is operated conveniently, simple process using above-mentioned gel polymer electrolyte assembled battery.
Polymer porous film in the present invention is handled by chemical crosslinking, and the chemical crosslinking structure of polyurethane-reinforcement is as follows:
(wherein: R=H, methyl, ethyl or propyl)
The step of preparation process of polymer porous film is as follows:
(a) polyvinyl formal or its homologue and organic solvent are dissolved according to mass ratio 1:5-1:20 organic
Solvent is configured to solution；
(b) two that polyvinyl formal or its homologue can be made to be chemically crosslinked are added into the solution of above-mentioned configuration
Isocyanates substance is 10:1-according to the mass ratio of polyvinyl formal or its homologue and diisocyanate species
2:1 stirs 30min；
(c) the non-molten of a certain proportion of Pioloform, polyvinyl acetal and its polyurethane-reinforcement product is added into the solution of above-mentioned configuration
Agent, according to polyvinyl formal or its homologue and Pioloform, polyvinyl acetal and its mass ratio for the non-solvent for being chemically crosslinked product
For 10:1-1:1, white micelle, which is precipitated, dissolves micelle by stirring；
(d) after the solution for being formulated above-mentioned steps uniformly coats, Pioloform, polyvinyl acetal and its polyurethane-reinforcement are immersed in
In the mixing bath of the non-solvent bath of product or its solvent and non-solvent, white film is precipitated；
(e) white film is dried to obtain polymer porous film.
The preferred N-Methyl pyrrolidone of organic solvent described in above-mentioned step of preparation process (a), N, N- dimethyl formyl
At least one of amine, chloroform, tetrahydrofuran, and according to similar compatibility principle and polyvinyl formal or its homology
The organic solvent of solubility difference≤1.7-2 of object；Diisocyanate species described in above-mentioned step of preparation process (b)
It is preferred that 4,4 '-methyl diphenylene diisocyanates, Toluene-2,4-diisocyanate, 4- diisocyanate, toluene 2,6- diisocyanate, hexa-methylene
At least one of diisocyanate, paraphenylene diisocyanate, isophorone diisocyanate；Above-mentioned step of preparation process (c)
Described in the preferred deionized water of non-solvent, anhydrous methanol, at least one of dehydrated alcohol；Above-mentioned step of preparation process (e)
Described in drying steps be that forced air drying or vacuum drying are carried out at 30 DEG C -60 DEG C.
Above-mentioned polymer porous film can be applicable in gel polymer electrolyte, polymer porous film absorption swelling electrolysis
Liquid realizes gelation, forms gel polymer electrolyte.Wherein, the main component of electrolyte is lithium salts, organic solvent.
Using the gel polymer electrolyte that above-mentioned polymer porous film is formed, lithium ion battery can be assembled.The lithium
Anode is at least one selected from following substance: LiFePO4, nickel-cobalt-manganese ternary material, spinelle mangaic acid in ion battery systems
Lithium, high capacity lithium-rich manganese base material, cathode are at least one selected from following substance: graphite, hard carbon, lithium titanate, silicon substrate chemical combination
Object and alloy.
Lithium salts is at least one selected from following substance: LiPF in electrolyte used in the lithium-ion battery system6、
LiClO4、LiBF4、LiAsF6、LiAlCl4、LiCF3SO3、LiN(SO2CF3)2、LiBOB、LiSbF6、LiSCN、LiSnF6、
LiGeF6、LiTaF6。
Organic solvent is at least one selected from following substance: carbon in electrolyte used in the lithium-ion battery system
Vinyl acetate, propene carbonate, butylene, vinylene carbonate, ethylene sulfite, propylene sulfite, sulfurous acid
Dimethyl ester, sulfurous acid diethyl ester, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate, acetic acid
Methyl esters, ethyl acetate, ethyl propionate, ethyl butyrate, tetrahydrofuran, 2- methyltetrahydrofuran, oxinane, dioxolanes, 1,
2- dimethoxy-ethane, diethylene glycol dimethyl ether, acetonitrile, dimethyl sulfoxide, acetone, N,N-dimethylformamide, sulfolane, diformazan
Base sulfone.
Gel polymer electrolyte layer, the anode that the lithium ion battery is mainly formed by polymer porous film of the invention
The components such as pole piece, cathode pole piece, positive pole ear, negative lug composition, the assembling mode of battery can be winding-type or laminated type,
The manufacturing method that i.e. lithium ion battery generallys use is all suitable for, and structural schematic diagram is as shown in Figure 1.
The invention has the following advantages that
The constituent Pioloform, polyvinyl acetal and its derivative of polymer porous film of the invention are non-stimulated, nontoxic, environment is friendly
It is good, it is nonflammable, highly-safe.For the polymer porous film of the technology of the present invention preparation by chemical crosslinking, chemical stability is good, will not
It is dissolved in the organic solvents such as carbonic ester, chemical stability.It the interconnected pore of polymer porous film can cracking absorption electrolysis
Liquid forms gel polymer electrolyte steady in a long-term existing as material of main part and support, this with Pioloform, polyvinyl acetal and its
Derivative as gelling agent causes the gelatinization of other systems, and there are essential distinctions.Polymer porous film of the invention including
Using carbonic ester as that will not be dissolved in the electrolyte system of primary solvent, and mechanical performance and all obtained with the compatibility of electrode
Improve.Therefore high chemical stability and mechanical strength are that battery process brings more convenience, do not need to utilize liquid electrolytic plastid
The diaphragm of system or other battery systems avoids now widely used gel polymer lithium ion battery septation as support
The use of component effectively reduces the number of interfaces in lithium ion battery structure, close to the average value 10 of liquid electrolyte‐3S/
cm。
Detailed description of the invention
Fig. 1 is the electric core structure of lithium battery of the gel polymer electrolyte layer formed using polymer porous film of the invention
Schematic diagram.
Fig. 2 is that process 4,4 '-methyl diphenylene diisocyanates (MDI) polyurethane-reinforcement prepared by embodiment 1 is chemically crosslinked
The microstructure figure of polyvinyl formal (PVFM) polymer porous film of processing.
Fig. 3 is polyvinyl butyral (PVB) polymer porous film of MDI chemical crosslinking processing prepared by embodiment 2
Microstructure figure.
Fig. 4 is the microstructure figure of polyvinyl formal (PVFM) polymer porous film prepared by comparative example 1.
Fig. 5 is after polymer porous film initiation prepared by embodiment 1 is gel polymer electrolyte, to be lied prostrate by linear scan
Pacify the electrochemical stability window result of test.
The charge and discharge cycles test result for the lithium ion battery that Fig. 6 is prepared for embodiment 8, voltage range 2.5V~4.25V,
Charge-discharge magnification 0.1C.
Specific embodiment
Parametric measurement of the invention is described below:
The measurement of imbibition rate
Gelation may be implemented by the PVFM perforated membrane that MDI is chemically crosslinked.In gelation process, electrolyte gradually soaks
The inside for entering polymer porous film, is swollen polymer, and transparence is gradually presented in white film.It impregnates in the electrolytic solution
After 30min, established gelatin polymer perforated membrane is taken out from electrolyte, is drained, and blots gelatin polymer with filter paper
The entrained electrolyte of porous film surface measures imbibition rate.
Imbibition rate=(liquid absorption amount/porous film quality) × 100%
Wherein, liquid absorption amount is the difference for the quality that perforated membrane impregnates before and after electrolyte.
The calculation method of conductivity
Gel polymer electrolyte to be measured is clamped with stainless steel substrates, forms the electricity of ┃ stainless steel ┃ GPE ┃ stainless steel ┃ structure
Pond measures its electrochemical interface impedance, according to the following formula can calculated for gel polymer film ionic conductivity σ:
σ=L/AR
Wherein, L is the thickness of polymer film, and A is the contact area of film and stainless steel working electrode, and R is gelatin polymer
The solution resistance of electrolyte.
Embodiment 1
0.1015g polyvinyl formal (PVFM) is dissolved in 1.0125g N-Methyl pyrrolidone (NMP), 45 DEG C
Magnetic agitation is all dissolved to PVFM, is added 0.0300g4 into solution, 4 '-methyl diphenylene diisocyanates (MDI), and 75 DEG C
Lower stirring 30min, then 0.1295g deionized water is added dropwise as Pioloform, polyvinyl acetal and its non-solvent of polyurethane-reinforcement product, analysis
White micelle out, the white micelle of agitated precipitation can dissolve, and continue magnetic agitation 30min, and mixed solution preparation finishes.It mixes molten
Liquid film immerses in deionized water, and porous membrane, the dry 1h of obtained perforated membrane is made.The method of dry perforated membrane is for example
It may be, but not limited to, perforated membrane is placed at 30 DEG C -60 DEG C, forced air drying or vacuum drying are passed through.Fig. 2 is embodiment 1
The microstructure of the PVFM polymer porous film of preparation, equally distributed interconnected pore bring high imbibition rate 593%.Implement
PVFM polymer porous film prepared by example 1 has high imbibition rate and high chemical stability, is to form stable gel electrolyte
Plastidome, and obtain the premise and basis of high conductance.PVFM polymer porous film prepared by embodiment 1 forms stable
The conductivity of gel electrolyte plastidome is 1.25 × 10‐3S/cm, the average value 10 of a little higher than liquid electrolyte conductivity‐3S/cm。
And the linear sweep voltammetry test result of Fig. 5 shows that PVFM polymer porous film prepared by embodiment 1 forms stable coagulate
The electrochemical stability window of glue electrolyte system is within the scope of 2.0V~5.0V, higher than the electrochemical stability window of liquid electrolyte
2.0V~4.3V, electrochemical stability are better than liquid electrolyte.
Embodiment 2
0.1049g polyvinyl butyral (PVB) is dissolved in 1.9975g N-Methyl pyrrolidone (NMP), 45 DEG C
Magnetic agitation is all dissolved to PVB, is added 0.0111g4 into solution, 4 '-methyl diphenylene diisocyanates (MDI), and 75 DEG C
Lower stirring 30min, then 0.0971g deionized water is added dropwise, white micelle is precipitated, the white micelle of agitated precipitation can dissolve, continue
Magnetic agitation 30min, mixed solution preparation finish.Mixed solution film immerses in deionized water, and porous membrane, gained is made
The dry 1h of the perforated membrane arrived.The method of dry perforated membrane for example may be, but not limited to, and perforated membrane is placed in 30 DEG C -60 DEG C
Under, pass through forced air drying or vacuum drying.Fig. 3 is the microstructure of PVB polymer porous film prepared by embodiment 2, uniformly
The interconnected pore of distribution brings high imbibition rate 610%.The high imbibition rate of PVB polymer porous film and high chemical stabilization
Property, it is the premise and basis to form stable gel electrolyte plastidome, and obtain high conductance.PVB prepared by embodiment 2 is poly-
Close the conductivity 1.33 × 10 that object perforated membrane forms stable gel electrolyte plastidome‐3S/cm, a little higher than liquid electrolyte electricity
The average value 10 of conductance‐3S/cm。
Embodiment 3
0.1012g polyvinyl formal (PVFM) is dissolved in 1.0343g N-Methyl pyrrolidone (NMP), 45 DEG C
Magnetic agitation is all dissolved to PVFM, is added 0.0315g4 into solution, 4 '-methyl diphenylene diisocyanates (MDI), and 75 DEG C
Lower stirring 30min, then 0.0114g deionized water is added dropwise, white micelle is precipitated, the white micelle of agitated precipitation can dissolve, continue
Magnetic agitation 30min, mixed solution preparation finish.Mixed solution film immerses in deionized water, and porous membrane, gained is made
The dry 1h of the perforated membrane arrived.The method of dry perforated membrane for example may be, but not limited to, and perforated membrane is placed in 30 DEG C -60 DEG C
Under, pass through forced air drying or vacuum drying.The PVFM polymer porous film of synthesis prepared by embodiment 3 has high imbibition rate
411% and high chemical stability, premise is provided for the stable formation of gel electrolyte plastidome and the acquisition of high conductance
Condition.PVFM polymer porous film prepared by embodiment 3 forms the conductance of the conductivity of stable gel electrolyte plastidome
Rate is 1.03 × 10‐3S/cm, close to the average value 10 of liquid electrolyte conductivity‐3S/cm。
Embodiment 4
0.0989g polyvinyl formal (PVFM) is dissolved in 0.9987g N-Methyl pyrrolidone (NMP), 45 DEG C
Magnetic agitation is all dissolved to PVFM, is added 0.0319g4 into solution, 4 '-methyl diphenylene diisocyanates (MDI), and 75 DEG C
Lower stirring 30min, then 0.1010g dehydrated alcohol is added dropwise, white micelle is precipitated, the white micelle of agitated precipitation can dissolve, continue
Magnetic agitation 30min, mixed solution preparation finish.Mixed solution film immerses in dehydrated alcohol, and porous membrane, gained is made
The dry 1h of the perforated membrane arrived.The method of dry perforated membrane for example may be, but not limited to, and perforated membrane is placed in 30 DEG C -60 DEG C
Under, pass through forced air drying or vacuum drying.PVFM polymer porous film prepared by embodiment 4 has high imbibition rate 352% and height
Chemical stability, provide precondition for the stable formation of gel electrolyte plastidome and the acquisition of high conductance.It is real
Apply the preparation of example 1 PVFM polymer porous film formed stable gel electrolyte plastidome conductivity conductivity for 0.97 ×
10‐3S/cm, close to the average value 10 of liquid electrolyte conductivity‐3S/cm。
Embodiment 5
0.1018g polyvinyl formal (PVFM) is dissolved in 0.7857g N-Methyl pyrrolidone (NMP), 45 DEG C
Magnetic agitation is all dissolved to PVFM, is added 0.0305g4 into solution, 4 '-methyl diphenylene diisocyanates (MDI), and 75 DEG C
Lower stirring 30min, then 0.1016g deionized water is added dropwise, white micelle is precipitated, the white micelle of agitated precipitation can dissolve, continue
Magnetic agitation 30min, mixed solution preparation finish.Mixed solution film immerses in deionized water, and porous membrane, gained is made
The dry 1h of the perforated membrane arrived.The method of dry perforated membrane for example may be, but not limited to, and perforated membrane is placed in 30 DEG C -60 DEG C
Under, pass through forced air drying or vacuum drying.The high chemical stability of PVFM polymer porous film prepared by embodiment 5 and high suction
Liquid rate 00% promotes the formation of stable gel electrolyte system, the conductivity 1.28 × 10 of system‐3S/cm, a little higher than liquid electricity
Solve the average value 10 of matter conductivity‐3S/cm。
Embodiment 6
0.0977g polyvinyl formal (PVFM) is dissolved in 0.9805g N-Methyl pyrrolidone (NMP), 45 DEG C
Magnetic agitation is all dissolved to PVFM, is added 0.0306g4 into solution, 4 '-methyl diphenylene diisocyanates (MDI), and 75 DEG C
Lower stirring 30min, then 0.0230g deionized water is added dropwise, white micelle is precipitated, the white micelle of agitated precipitation can dissolve, continue
Magnetic agitation 30min, mixed solution preparation finish.Mixed solution film immerses in deionized water, and porous membrane, gained is made
The dry 1h of the perforated membrane arrived.The method of dry perforated membrane for example may be, but not limited to, and perforated membrane is placed in 30 DEG C -60 DEG C
Under, pass through forced air drying or vacuum drying.The high chemical stability of PVFM polymer porous film prepared by embodiment 6, Yi Jigao
Imbibition rate 485% promotes the formation of stable gel electrolyte system, the conductivity 1.12 × 10 of system‐3S/cm, a little higher than liquid
The average value 10 of electrolytic conductivity‐3S/cm。
Although it should be noted that only giving in embodiment using polyvinyl formal and polyvinyl butyral system
Standby polymer porous film of the invention, it will be appreciated by those skilled in the art that polyvinyl formal and its homologue all have
(1)-(4) basic structural unit as described in specification summary of the invention, key structural feature is similar, while all having certain hydroxyl
Base group can form the chemical crosslinking structure of the polyurethane-reinforcement for the Inventive polymers perforated membrane listed in Summary,
Therefore polymer porous film of the invention can be prepared using other homologues of polyvinyl formal.Although the present invention is real
Apply example only describe it is preferred using N-Methyl pyrrolidone (NMP) polyethylene dissolving alcohol formal or its homologue, organic solvent
At least one of N-Methyl pyrrolidone, n,N-Dimethylformamide, chloroform, tetrahydrofuran, those skilled in the art
Member should appreciate that according to similar compatibility principle and the solubility difference of polyvinyl formal or its homologue≤1.7-2
Organic solvent is also feasible.Except 4,4 '-methyl diphenylene diisocyanates (MDI), any other can also be used
Diisocyanate lipid material to be chemically crosslinked with polyvinyl formal or its homologue.In addition to preferred deionized water,
It, can also be to polyvinyl formal or its homologue and two outside these non-solvents cheap and easy to get of anhydrous methanol, dehydrated alcohol
Other polyvinyl formals or the non-solvent of its homologue polyurethane-reinforcement product are added dropwise in the solution of isocyanates configuration.
The mass ratio of polyvinyl formal or its homologue and its organic solvent can be any one ratio between 1:5-1:20.
The mass ratio of polyvinyl formal or its homologue and diisocyanates can be any ratio between 10:1-2:1.It is poly-
Vinyl formal or its homologue and Pioloform, polyvinyl acetal and its mass ratio for being chemically crosslinked the non-solvent of product are 10:1-
Any ratio between 1:1.
Comparative example 1
0.1953g polyvinyl formal (PVFM) is dissolved in 2.0156g N-Methyl pyrrolidone (NMP), 45 DEG C
Lower magnetic agitation is all dissolved to PVFM, and 0.1980g deionized water is added into solution, and white micelle is precipitated, continues at 45 DEG C
Magnetic agitation is dissolved to precipitate.It by above-mentioned solution coating, immerses in deionized water, porous membrane is made, it is obtained porous
Film dries 1h.Fig. 4 is the microstructure figure for preparing polymer porous film, and perforated membrane is presented porous honeycomb, is about with diameter
25 μm of macrovoid is formed and is also distributed on macroporous polymer wall more uniformly, the fine pore that diameter is about 1-2 μm.Without
The PVFM polymer porous film of chemical crosslinking can be quickly soluble in the electrolyte comprising organic solvent such as LiPF6/EC+DMC(3:
7in Vol.), stable gel electrolyte plastidome can not be formed.
Imbibition rate and Conductivity Ratio compared with
| Sample | Imbibition rate | Conductivity |
| Embodiment 1 | 593% | 1.25×10‐3 |
| Embodiment 2 | 610% | 1.33×10‐3 |
| Embodiment 3 | 411% | 1.03×10‐3 |
| Embodiment 4 | 352% | 0.97×10‐3 |
| Embodiment 5 | 600% | 1.28×10‐3 |
| Embodiment 6 | 485% | 1.12×10‐3 |
| Comparative example 1 | Dissolution | ‐ |
By comparing discovery, for the constituent of polymer porous film of the invention by chemical crosslinking, chemical stability is good, gathers
Closing object perforated membrane will not be dissolved in the Elements in Organic Solvents of electrolyte.It the interconnected pore of perforated membrane can cracking absorption electrolysis
Liquid effectively prevent the omission of electrolyte after forming gel polymer electrolyte.Gel polymer electrolyte conductivity is high simultaneously,
Reach and close to liquid electrolyte conductivity average value 1.12 × 10‐3。
Embodiment 7
The polymer porous film that embodiment 1 is prepared is immersed in 1mol/L LiPF6It is dissolved in EC:DMC=3:7 (V/
V) in electrolyte, or to polyalcohol stephanoporate film surface be added dropwise few drops of lithium-ion battery electrolytes.Perforated membrane absorption swelling electrolyte
Afterwards, gel polymer electrolyte is obtained, is avoided using the diaphragm element that must be placed in previous gel polymer lithium ion battery,
The number of interfaces in lithium ion battery structure is effectively reduced, is conducive to improve ionic conductivity.It is surveyed by linear sweep voltammetry
Examination, it is known that electrochemical stability window 2.0V~5.0V of this kind of gel polymer electrolyte, result are as shown in Figure 5；Pass through friendship
Flow impedance test, solution resistance are 5.0 Ω, and calculating conductivity according to aforementioned formula is 1.25 × 10‐3S/cm.Used electrolysis
The main component of liquid is lithium salts and organic solvent.Lithium salts is selected from least one of following substance: LiPF6、LiClO4、LiBF4、
LiAsF6、LiAlCl4、LiCF3SO3、LiN(SO2CF3)2、LiBOB、LiSbF6、LiSCN、LiSnF6、LiGeF6、LiTaF6.It is organic
Solvent is selected from least one of following substance: ethylene carbonate, propene carbonate, butylene, vinylene carbonate, Asia
Sulfuric acid vinyl ester, propylene sulfite, dimethyl sulfite, sulfurous acid diethyl ester, gamma-butyrolacton, dimethyl carbonate, carbonic acid two
Ethyl ester, methyl ethyl carbonate, methyl formate, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, tetrahydrofuran, 2- methyl
Tetrahydrofuran, oxinane, dioxolanes, 1,2- dimethoxy-ethane, diethylene glycol dimethyl ether, acetonitrile, dimethyl sulfoxide, third
Ketone, N,N-dimethylformamide, sulfolane, dimethyl sulfone.
Embodiment 8
With LiFePO4For anode, Li is cathode, assembles half-cell.Battery uses CR2032 button cell.Do not add in battery
Add diaphragm element, replace, using polymer porous film prepared by embodiment 1.In an assembling process, a small amount of electrolysis is added dropwise
Liquid infiltrates polymer porous film mutually with electrode material, and is swollen electrolyte and makes its gelation.Using prepared by embodiment 1
Polymer porous film is applied to gel polymer electrolyte, and half electricity assembled using LiFePO4 as positive battery
Pond, it is as shown in FIG. 6 the result shows that being applied to using polymer porous film prepared by embodiment 1 solidifying by charge-discharge test
The chemical stability of xanthan polymer electrolyte is good, and the cyclical stability of battery is excellent, and circulating battery 80 times, capacity retention ratio reaches
95.4%, it is recycled 80 times close to using liquid electrolyte, the application effect of capacity retention ratio 97.6% has reached in battery system
Application requirement.
Polymer porous film prepared by embodiment 1 can also be used to be made of other materials the lithium-ion electric of positive and negative anodes
Pond.Such as the anode of lithium ion battery is at least one selected from following substance: LiFePO4, nickel-cobalt-manganese ternary material, point are brilliant
Stone LiMn2O4, high capacity lithium-rich manganese base material, cathode are at least one selected from following substance: graphite, hard carbon, lithium titanate, silicon
Based compound and alloy.
Fig. 1 is shown using polymer porous film of the invention as the obtained lithium ion battery of gel polymer electrolyte
One embodiment of core strueture.The lithium ion battery cell is laminated type or winding-type, including anode pole piece 1, is welded on just
The positive pole ear 2 of one end of pole pole piece 1, cathode pole piece 3 and be welded on cathode pole piece 3 and 2 phase the same end of positive pole ear
Negative lug 4 and the gel polymer electrolyte layer formed by polymer porous film of the invention between positive and negative anodes pole piece
5.It will be appreciated by those skilled in the art that the structure that solid electrolyte lithium ion battery generallys use is suitable for using the present invention
Polymer porous film as the obtained lithium ion battery of gel polymer electrolyte.
It is being discharged using polymer porous film of the invention as the obtained lithium ion battery of gel polymer electrolyte
In the process, lithium ion deintercalation from the structure of 3 active material of cathode pole piece, in 3 active material of cathode pole piece and gelatin polymer
Solvation occurs on the interface of electrolyte layer 5, migration reaches 1 side of anode pole piece in gel polymer electrolyte layer 5,
Pass through desolvation on the interface of 1 active material of anode pole piece and gel polymer electrolyte layer 5, then is embedded into anode pole piece
In the structure of 1 material, and electronics reaches positive pole ear 2 via external circuit by negative lug 4, and the displacement for forming electronics is i.e. electric
Stream.During the charging process, with the above process on the contrary, lithium ion deintercalation from 1 active material of anode pole piece, passes through gelatin polymer
After the interface of electrolyte layer 5 and anode pole piece 1 and cathode pole piece 3, it is embedded into the structure of 3 active material of cathode pole piece.
It is different from liquid electrolyte lithium ion battery, for gel polymer lithium ion battery, due to using tool
There is the polymer porous film absorption-of certain mechanical strength to be swollen the gel polymer electrolyte formed after electrolyte, avoids making
With diaphragm, reduces the obstruction that multiple interfaces and diaphragm during lithium ion mobility generate it, be more advantageous to lithium ion
Migration, reduce lithium ion battery internal resistance.The shape of battery is not limited by liquid electrolyte simultaneously, can be according to design requirement
Production.
Claims (21)
1. a kind of polymer porous film, which is characterized in that the group of the polymer porous film be divided into polyvinyl formal or its
The chemical crosslinking product of at least one of homologue and diisocyanate species, wherein the polymer porous film is to have three
The porous form membrane for tieing up netted structure exists.
2. a kind of polymer porous film, which is characterized in that the group of the polymer porous film be divided into polyvinyl formal or its
The chemical crosslinking product of at least one of homologue and diisocyanate species, wherein the chemistry of the polymer porous film is handed over
It is as follows to be coupled structure:
(wherein: R=H, methyl, ethyl or propyl).
3. a kind of preparation method of polymer porous film, which is characterized in that following works are passed through in the preparation of the polymer porous film
Skill step:
(1) polyvinyl formal or its homologue 1:5-1:20 in mass ratio are dissolved in organic solvent, are configured to solution；
(2) being added in the solution prepared to step (1) can be such that the polyvinyl formal or its homologue is chemically crosslinked
Diisocyanate species, stirring to the diisocyanate species dissolve, wherein the polyvinyl formal or its
The mass ratio of homologue and the diisocyanate species is 10:1-2:1；
(3) polyvinyl formal or its homologue and polyvinyl alcohol contracting are added in the solution prepared to step (2)
The non-solvent of the chemical crosslinking product of formaldehyde or its homologue, is precipitated white micelle, by stirring, dissolves the micelle,
In, the chemical crosslinking product of the polyvinyl formal or its homologue and the polyvinyl formal or its homologue and
The mass ratio of the non-solvent is 10:1-1:1；
(4) after the solution that step (3) is formulated uniformly being coated, be immersed in the polyvinyl formal or its homologue and
The non-solvent bath of the chemical crosslinking product of the polyvinyl formal or its homologue or the mixing bath of its solvent and non-solvent
In, white film is precipitated；
(5) white film is dried to obtain the polymer porous film.
4. a kind of preparation method of polymer porous film according to claim 3, which is characterized in that organic solvent is foundation
Organic solvent of the solubility difference less than 2 of similar compatibility principle and the polyvinyl formal or its homologue.
5. a kind of preparation method of polymer porous film according to claim 3, which is characterized in that organic solvent is foundation
Organic solvent of the solubility difference less than 1.7 of similar compatibility principle and the polyvinyl formal or its homologue.
6. a kind of preparation method of polymer porous film according to claim 3, which is characterized in that organic solvent is foundation
Similar compatibility principle and the solubility difference of the polyvinyl formal or its homologue are equal to the organic solvent of 1.7-2.0.
7. a kind of preparation method of polymer porous film according to claim 3, which is characterized in that organic solvent is N- first
At least one of base pyrrolidones, N,N-dimethylformamide, chloroform, tetrahydrofuran.
8. a kind of preparation method of polymer porous film according to claim 3, which is characterized in that the diisocyanate
Substance is 4,4 '-methyl diphenylene diisocyanates, Toluene-2,4-diisocyanate, 4- diisocyanate, toluene 2,6- diisocyanate, six Asias
At least one of methyl diisocyanate, paraphenylene diisocyanate and isophorone diisocyanate.
9. a kind of preparation method of polymer porous film according to claim 3, which is characterized in that non-solvent is deionization
At least one of water, anhydrous methanol and dehydrated alcohol.
10. a kind of preparation method of polymer porous film according to claim 3, which is characterized in that the drying steps
To carry out forced air drying or vacuum drying at 30 DEG C -60 DEG C.
11. a kind of lithium ion battery for having used polymer porous film according to claim 1, the lithium-ion electric pond body
Anode in system is at least one selected from following substance: LiFePO4, nickel-cobalt-manganese ternary material, spinel lithium manganate and Gao Rong
Measure lithium-rich manganese base material, the cathode in the lithium-ion battery system is at least one selected from following substance: graphite, hard carbon,
Lithium titanate, silicon base compound and alloy.
12. a kind of application of polymer porous film according to claim 1 in gel polymer electrolyte, feature exist
In the polymer porous film absorption swelling electrolyte realizes gelation, forms gel polymer electrolyte, wherein the electricity
The main component for solving liquid is lithium salts and organic solvent.
13. application according to claim 12, which is characterized in that the lithium salts is at least one selected from following substance:
LiPF6、LiClO4、LiBF4、LiAsF6、LiAlCl4、LiCF3SO3、LiN(SO2CF3)2、LiBOB、LiSbF6、LiSCN、
LiSnF6、LiGeF6、LiTaF6。
14. application as claimed in claim 12, which is characterized in that the organic solvent is at least one selected from following substance
Kind: ethylene carbonate, propene carbonate, butylene, vinylene carbonate, ethylene sulfite, propylene sulfite, Asia
Dimethyl suflfate, sulfurous acid diethyl ester, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl formate,
Methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, tetrahydrofuran, 2- methyltetrahydrofuran, oxinane, dioxy penta
Ring, 1,2- dimethoxy-ethane, diethylene glycol dimethyl ether, acetonitrile, dimethyl sulfoxide, acetone, N,N-dimethylformamide, ring fourth
Sulfone, dimethyl sulfone.
15. a kind of battery core for the lithium ion battery for having used polymer porous film according to claim 1, the battery core packet
It includes:
Anode pole piece and the positive pole ear welded on the anode pole piece；
Cathode pole piece and the negative lug welded on the cathode pole piece；
Gel polymer electrolyte layer between the anode pole piece and the cathode pole piece, the gel polymer electrolyte
Matter layer is formed using polymer porous film described in claim 1.
16. battery core according to claim 15, wherein the battery core of the lithium ion battery is laminated type or winding-type.
17. a kind of lithium ion battery including battery core described in claim 15 or 16.
18. a kind of lithium ion battery for having used polymer porous film according to claim 1.
19. a kind of application of polymer porous film according to claim 1 in gel polymer electrolyte, feature exist
In the polymer porous film absorption swelling electrolyte realizes gelation, forms gel polymer electrolyte.
20. a kind of battery core for the lithium ion battery for having used polymer porous film according to claim 1, the battery core packet
It includes:
Gel polymer electrolyte layer, the gel polymer electrolyte layer use polymer porous film described in claim 1
It is formed.
21. a kind of lithium ion battery including the battery core described in claim 20.
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| CN201310231733.1A CN103804892B (en) | 2012-11-09 | 2013-06-09 | A kind of polymer porous film and preparation method thereof and the application in gel polymer electrolyte |
| PCT/IB2013/002452 WO2014072789A2 (en) | 2012-11-09 | 2013-11-05 | Porous polymer membrane, preparation method therefor, and use of same in gel polymer electrolyte |
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| CN201310231733.1A CN103804892B (en) | 2012-11-09 | 2013-06-09 | A kind of polymer porous film and preparation method thereof and the application in gel polymer electrolyte |
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| CN105161759B (en) * | 2015-08-21 | 2017-10-10 | 北京科技大学 | A kind of composite electrolyte of lithium-air battery and preparation method thereof |
| KR102019312B1 (en) * | 2016-02-25 | 2019-09-06 | 주식회사 엘지화학 | Composition for gel polymer electrolyte and lithium secondary battery comprising the same |
| KR102133384B1 (en) * | 2016-09-02 | 2020-07-14 | 주식회사 엘지화학 | Gel polymer electrolyte and lithium secondary battery comprising the same |
| CN106374139B (en) * | 2016-11-04 | 2018-08-28 | 北京大学 | A kind of gel electrolyte materials monomer, polymer, preparation method and applications |
| EP3442070A1 (en) * | 2017-08-10 | 2019-02-13 | Baden-Württemberg Stiftung gGmbH | Polyhydroxyurethane-based gel polymer electrolytes for energy storage systems |
| CN113140789B (en) * | 2021-04-22 | 2022-09-09 | 北京化工大学 | Recyclable self-repairing gel-state electrolyte and preparation method and application thereof |
| CN114725500A (en) * | 2022-04-11 | 2022-07-08 | 万向一二三股份公司 | Polymer composite solid electrolyte and preparation method thereof |
| CN115133122B (en) * | 2022-08-29 | 2022-11-04 | 江苏展鸣新能源有限公司 | Preparation method and application of lithium ion battery electrolyte |
| WO2024168812A1 (en) * | 2023-02-17 | 2024-08-22 | 宁德时代新能源科技股份有限公司 | Aldehyde-ketone polymer, electrode sheet and related battery cell, battery, and electric device |
| CN117374515B (en) * | 2023-12-06 | 2024-04-19 | 天津力神电池股份有限公司 | Separator with lithium ion capacity compensation function, preparation method thereof and battery |
| CN118336151B (en) * | 2024-06-12 | 2024-09-17 | 超威电源集团有限公司 | Self-healing aqueous gel battery and preparation method thereof |
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| JPS5874756A (en) * | 1981-10-27 | 1983-05-06 | Fujikura Ltd | Polyvinyl formal coating |
| JP4038189B2 (en) * | 2004-04-21 | 2008-01-23 | 電気化学工業株式会社 | Sheet |
| JP4878290B2 (en) * | 2005-01-14 | 2012-02-15 | 三井化学株式会社 | Polyvinyl acetal resin varnish, gelling agent, non-aqueous electrolyte and electrochemical device |
| WO2006098240A1 (en) * | 2005-03-14 | 2006-09-21 | Sony Corporation | Polymer electrolyte and battery |
| WO2010101170A1 (en) * | 2009-03-05 | 2010-09-10 | 株式会社村田製作所 | Dielectric resin composition for film capacitor, process for producing same, and film capacitor |
| CN102035043B (en) * | 2009-09-25 | 2014-02-12 | 上海比亚迪有限公司 | Polymer porous membrane, preparation method thereof, polymer electrolyte, polymer battery and preparation method of battery |
| JP2011195696A (en) * | 2010-03-19 | 2011-10-06 | Denki Kagaku Kogyo Kk | Isocyanate-modified polyvinyl acetal resin and method for producing the same |
| CN102199846A (en) * | 2011-04-29 | 2011-09-28 | 华南师范大学 | Porous polymer electrolyte supporting membrane material, preparation method thereof and application thereof |
| CN102504162B (en) * | 2011-11-17 | 2013-09-18 | 中山大学 | Preparation methods for hyper branched polyurethane sulfonate and solid polymer electrolyte film of hyper branched polyurethane sulfonate |
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