WO2014072789A2 - Membrane polymère poreuse, son procédé de préparation, et son utilisation dans un électrolyte gel polymère - Google Patents

Membrane polymère poreuse, son procédé de préparation, et son utilisation dans un électrolyte gel polymère Download PDF

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WO2014072789A2
WO2014072789A2 PCT/IB2013/002452 IB2013002452W WO2014072789A2 WO 2014072789 A2 WO2014072789 A2 WO 2014072789A2 IB 2013002452 W IB2013002452 W IB 2013002452W WO 2014072789 A2 WO2014072789 A2 WO 2014072789A2
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diisocyanate
electrolyte
polymer
porous film
polymer porous
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PCT/IB2013/002452
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Chinese (zh)
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WO2014072789A3 (fr
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连芳
任岩
关红艳
文炎
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约翰逊控制技术公司
北京科技大学
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Publication of WO2014072789A3 publication Critical patent/WO2014072789A3/fr

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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
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the technical field of preparation and application of polymer films, in particular to a polymer porous film and a preparation method thereof, and a stable system for adsorbing and swelling an electrolyte as a gel polymer electrolyte: Background Art
  • Gel polymer is widely used as a gel polymer electrolyte system instead of a liquid electrolyte of a lithium ion battery, and has a high ion conductivity close to that of a liquid electrolyte, and has a characteristic that the solid electrolyte does not leak. It can solve the high volatility and flammability of organic electrolytes, and may cause safety problems such as cracking, fire and explosion in case of short circuit. It provides guarantee for the application of large-scale lithium-ion batteries in the field of new energy vehicles and solar energy and wind energy energy storage equipment.
  • PEO polyoxyethylene
  • PA polyacrylonitrile
  • PMMA polymethyl methacrylate
  • P VDF polyvinylidene fluoride
  • the PEO-based gel polymer electrolyte is easy to crystallize, resulting in low electrical conductivity at room temperature.
  • the interface between the gel polymer film and the lithium electrode in the PAN-based gel polymer electrolyte is severely deactivated, and the mechanical properties are degraded when the plasticizer content is high. It is more serious;
  • PMMA-based gel polymer electrolyte has poor mechanical properties;
  • PVDF-based gel polymer electrolyte has a regular polymer structure and is easy to crystallize, which is not conducive to ion conduction. It can be seen that there are widespread problems with commonly used gel polymer bases, and gel film stability, mechanical properties and compatibility with electrodes still need to be improved. In addition, the problem of oozing out of the electrolyte from the gel has not been properly solved. Summary of the invention
  • Hiroshi Sugawara et al. mentioned that the ratio of vinyl alcohol units in polyvinyl acetal is reduced by acid modification, and acid modification not only causes intramolecular exchange reaction of acetal ring, but also is isolated.
  • the vinyl alcohol unit becomes a plurality of linked structures, thereby improving the gelation performance of the organic solvent.
  • the polyvinyl acetal-based polymer has a good prospect for application to a lithium ion battery gel polymer, but the polyvinyl acetal and its derivative have high solubility in an organic solvent such as a carbonate, and are not stable, so When the gel polymer electrolyte is prepared by the in-situ polymerization process, the separator member must be placed, resulting in an increase in the interface.
  • Li Fangxing et al. prepared a cross-linked polyvinyl acetal polyurethane which can dissolve the network, in which dibutyltin dilaurate or dilauric acid was used as a catalyst, and 4,4'- Diphenylmethane diisocyanate (MDI) chemically crosslinks polyvinyl acetal into a network structure, which is soluble in coatings, paints, adhesives, and the like.
  • MDI 4,4'- Diphenylmethane diisocyanate
  • the object of the present invention is to provide a porous film of polyvinyl acetal and a derivative thereof, and a method for producing the same, which are chemically crosslinked into a three-dimensional network-like stable structure.
  • the polymer porous film exhibits the advantages of excellent film formability, heat resistance, good water resistance, and relatively stable chemical structure of the polyvinyl acetal and its derivatives, and the above polymer porous film and preparation thereof.
  • the method solves the problem that the polyvinyl acetal and its derivative have high solubility in an organic solvent such as carbonate and cannot be stably existed, and the chemical stability is remarkable. Improve.
  • the above polymer porous membrane has good ability of adsorbing electrolyte, and the liquid absorption rate is up to
  • the gelation of the system is achieved by adsorbing and swelling the electrolyte (including a carbonate-based electrolyte system), and the porous membrane and the gel system can be stably existed for a long period of time.
  • the electrolyte including a carbonate-based electrolyte system
  • the polymer porous film to a gel polymer electrolyte, particularly to a gel polymer lithium ion battery. Since the polymer porous membrane and the formed gel polymer electrolyte can be stably existed for a long period of time, there is no problem of dissolution of the polymer porous membrane in the system and electrolyte leakage, and the above polymer porous membrane will swell in the electrolyte.
  • the polymer porous membrane can be obtained in the gel polymer electrolyte, and can be obtained with respect to the solid electrolyte. High conductivity. With respect to the liquid electrolyte, the polymer porous film does not cause a liquid leakage problem in the liquid electrolyte when applied to the gel polymer electrolyte, and at the same time, a conductivity substantially equal to that of the liquid electrolyte can be obtained, and the polymer is obtained.
  • the use of a porous membrane for a gel polymer electrolyte facilitates battery assembly.
  • polyvinyl acetal and its derivatives have conventionally been used as binders and have good bonding properties.
  • the polymer porous film according to the present invention exhibits good adhesion properties of polyvinyl acetal and its derivatives, and therefore, the gel polymer electrolyte formed of the above polymer porous film has a polymer porous film as compared with other polymer porous films Excellent adhesion and compatibility with the electrode, reducing the electrochemical polarization of the interface, high electrochemical stability, and the electrical conductivity is close to the average value of the liquid electrolyte conductivity of 10-3 ⁇ 4/cm. Moreover, it has high mechanical properties, and the assembled battery using the gel polymer electrolyte is convenient to operate and simple in process.
  • the polymer porous membrane of the present invention is subjected to chemical crosslinking treatment, and the chemically crosslinked structure of the polyurethane is as follows:
  • the preparation steps of the polymer porous membrane are as follows:
  • the organic solvent described in the above preparation step (a) is preferably at least one of N-methylpyrrolidone, hydrazine, hydrazine-dimethylformamide, chloroform, tetrahydrofuran, and polyethylene according to a similar compatibility principle.
  • the diisocyanate material described in the above production process step (b) is preferably 4,4'-diphenylmethane diisocyanate or toluene-2.
  • the solvent is preferably at least one of deionized water, anhydrous methanol, and anhydrous ethanol; the drying step described in the preparation step (e) is blast drying or vacuum drying at 30 ° C - 60 ° C. .
  • the above polymer porous film can be applied to a gel polymer electrolyte, and the polymer porous film adsorbs and swells the electrolyte to effect gelation to form a gel polymer electrolyte.
  • the main component of the electrolytic solution is a lithium salt or an organic solvent.
  • a lithium ion battery can be assembled by using the gel polymer electrolyte formed of the above polymer porous film.
  • the positive electrode in the lithium ion battery system is at least one selected from the group consisting of lithium iron phosphate, nickel cobalt manganese ternary material, spinel lithium manganate, high capacity lithium-rich manganese-based material, and the negative electrode is selected from the following materials. At least one of: graphite, hard carbon, lithium titanate, silicon based compounds and alloys.
  • the lithium salt in the electrolyte used in the lithium ion battery system is at least one selected from the group consisting of LiPF 6 , LiC 10 4 , LiBF 4 , LiAsF 6 , LiAlCl 4 , LiCF 3 S ⁇ 3 , LiN (S ⁇ 2 CF 3 ) 2 LiBOB, LiSbF 6 , LiSCN, LiSnF 6 , LiGeF 6 , LiTaF 6 .
  • the organic solvent in the electrolyte used in the lithium ion battery system is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinyl sulfite, sulfurous acid.
  • Propylene ester dimethyl sulfite, diethyl linoleate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, ethyl acetate, Ethyl propionate, ethyl butyrate, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, dioxolane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, acetonitrile, two Sulfoxide, acetone, hydrazine, hydrazine-dimethylformamide, sulfolane, dimethyl
  • the lithium ion battery is mainly composed of a gel polymer electrolyte layer formed by the polymer porous film of the present invention, a positive electrode pole piece, a negative electrode pole piece, a positive electrode tab, a negative electrode tab, and the like, and the battery can be assembled in a winding type. Or a laminated type, that is, a manufacturing method generally used for a lithium ion battery, and a schematic structural view thereof is shown in FIG.
  • the invention has the following advantages:
  • the polyvinyl acetal and its derivative of the polymer porous film of the present invention are non-irritating, non-toxic, environmentally friendly, non-flammable, and highly safe.
  • the porous polymer membrane prepared by the technique of the present invention is chemically crosslinked, has good chemical stability, is not dissolved in an organic solvent such as carbonate, and is chemically stable.
  • the interconnected pores of the polymer porous membrane can quickly adsorb the electrolyte, and form a long-term stable gel polymer electrolyte as a host material and support. This is related to polyvinyl acetal and its derivatives as a gelling agent. There is an essential difference in the gelation process.
  • the polymer porous film of the present invention does not dissolve in an electrolyte system including a carbonate as a main solvent, and both mechanical properties and compatibility with electrodes are improved. Therefore, high chemical stability and mechanical strength bring greater convenience to the battery process, and do not require the use of a liquid electrolyte system or a separator of other battery systems as a support, thereby avoiding widespread use at present.
  • the use of a diaphragm member in a gel polymer lithium ion battery effectively reduces the number of interfaces in the lithium ion battery structure, which is close to the average value of the liquid electrolyte of 10 - 3 S/cm.
  • Fig. 1 is a view showing the structure of a lithium battery cell of a gel polymer electrolyte layer formed by using the polymer porous film of the present invention.
  • Fig. 2 is a view showing the appearance of a polyvinyl formal (PVFM polymer porous film) by chemically crosslinking 4,4'-diphenylmethane diisocyanate (MDI) prepared in Example 1.
  • PVFM polyvinyl formal
  • MDI 4,4'-diphenylmethane diisocyanate
  • Fig. 3 is a microscopic top view of a polyvinyl butyral (PVB) polymer porous film of MDI chemically crosslinked prepared in Example 2.
  • PVB polyvinyl butyral
  • Fig. 4 is a view showing the appearance of a polyvinyl formal (PVFM) polymer porous film prepared in Comparative Example 1.
  • PVFM polyvinyl formal
  • Figure 5 is a graph showing the results of an electrochemical stabilization window by linear sweep voltammetry after the polymer porous membrane prepared in Example 1 was initiated as a gel polymer electrolyte.
  • Fig. 6 shows the results of charge and discharge cycle test of the lithium ion battery prepared in Example 8, with a voltage range of 2.5 V to 4.25 V and a charge and discharge rate of 0.1 C. detailed description
  • Gelation can be achieved by MDI chemically crosslinked PVFM porous membranes.
  • the electrolyte gradually immersed in the interior of the polymer porous membrane to swell the polymer, and the white film gradually became transparent.
  • the formed gel polymer porous film was taken out from the electrolytic solution, drained, and the residual electrolyte on the surface of the gel polymer porous film was blotted with a filter paper to measure the liquid absorption rate.
  • the gel polymer electrolyte to be tested was clamped with a stainless steel sheet to form a battery of I stainless steel I GPE I stainless steel I structure, and the electrochemical interface impedance was measured.
  • PVFM polyvinyl formal
  • MP N-methylpyrrolidone
  • MDI diisocyanate
  • FIG. 1 is a microscopic appearance of the PVFM polymer porous membrane prepared in Example 1, and the uniformly distributed interconnected pores brought a high liquid absorption rate of 593%.
  • the PVFM polymer porous membrane prepared in Example 1 has high liquid absorption rate and high chemical stability, and is a prerequisite and basis for forming a stable gel electrolyte system and obtaining high electrical conductivity.
  • the conductivity of the gel electrolyte systems PVFM porous polymer membrane prepared in Example 1 was formed a stable 1.25 X l (X 3 S / cm, the conductivity of the liquid electrolyte is slightly higher than the average 1CT 3 S / C m.
  • the linear sweep voltammetry test results of Figure 5 show that the electrochemical stability window of the stable gel electrolyte system formed by the PVFM polymer porous membrane prepared in Example 1 is in the range of 2.0V ⁇ 5.0V, which is higher than that of the liquid electrolyte.
  • the chemical stability window is 2.0V ⁇ 4.3V, and the electrochemical stability is better than that of the liquid electrolyte.
  • PVB polyvinyl butyral
  • NMP N-methylpyrrolidone
  • MDI Methane diisocyanate
  • the white micelles were dissolved by stirring to dissolve, and magnetic stirring was continued for 30 min.
  • the mixed solution was prepared. The mixed solution was coated with a film and immersed in deionized water to prepare a porous film, and the obtained porous film was dried for 1 hour.
  • the method of drying the porous film may be, for example, but not limited to, placing the porous film at 30 ° C - 60 ° C, by air drying or vacuum drying.
  • 3 is a microscopic morphology of the PVB polymer porous film prepared in Example 2, and the uniformly distributed interconnected pores bring a high liquid absorption rate of 610%.
  • the high liquid absorption rate and high chemical stability of the PVB polymer porous membrane form a stable gel electrolyte system and obtain higher electricity.
  • the PVB polymer porous membrane prepared in Example 2 formed a stable gel electrolyte system having a conductivity of 1.33 X 10- 3 S/cm, which is slightly higher than the average value of the liquid electrolyte conductivity of 10 - 3 S/cm.
  • Example 3
  • PVFM polyvinyl formal
  • NMP N-methylpyrrolidone
  • MDI diisocyanate
  • the mixed solution was coated with a film, immersed in deionized water to prepare a porous film, and the obtained porous film was dried for 1 hour.
  • the method of drying the porous film may be, for example, but not limited to, placing the porous film at 30 ° C - 60 ° C, by air drying or vacuum drying.
  • the synthetic PVFM polymer porous membrane prepared in Example 3 has a high liquid absorption rate of 411% and high chemical stability, and provides a prerequisite for stable gel electrolyte system formation and high electrical conductivity.
  • the conductivity of the stabilized gel electrolyte system formed by the PVFM polymer porous film prepared in Example 3 had an electrical conductivity of 1.03 ⁇ 10 ⁇ 3 S/cm, which was close to the average value of the liquid electrolyte conductivity of 10 ⁇ / ⁇ .
  • Example 4
  • PVFM polyvinyl formal
  • NMP N-methylpyrrolidone
  • MDI diisocyanate
  • OJ OlOg anhydrous ethanol was added dropwise to precipitate a white micelle.
  • the white micelle was dissolved by stirring to dissolve, and the magnetic stirring was continued for 30 min.
  • the mixed solution was prepared.
  • the mixed solution was coated with a film, immersed in absolute ethanol to prepare a porous film, and the obtained porous film was dried for 1 hour.
  • the method of drying the porous film may be, for example, but not limited to, placing the porous film at 30 ° C - 60 ° C, by air drying or vacuum drying.
  • the PVFM polymer porous membrane prepared in Example 4 has a high liquid absorption rate of 352% and high chemical stability, and provides a prerequisite for the formation of a stable gel electrolyte system and the acquisition of higher electrical conductivity.
  • the conductivity of the stabilized gel electrolyte system formed by the PVFM polymer porous membrane prepared in Example 1 had an electrical conductivity of 0.97 X 10- 3 S/cm, which was close to the average value of the liquid electrolyte conductivity of 10 _ 3 S/cm.
  • Example 5
  • PVFM polyvinyl formal
  • NMP N-methylpyrrolidine
  • MDI 4,4'-diphenylmethane diisocyanate
  • the method of drying the porous film may be, for example, but not limited to, placing the porous film at 30 ° C - 60 ° C, by air drying or vacuum drying.
  • the high chemical stability of the PVFM polymer porous membrane prepared in Example 5 and the high liquid absorption rate of 00% promoted the formation of a stable gel electrolyte system.
  • the electrical conductivity of the system was 1.28 X 10- 3 S/cm, slightly higher than that of the liquid electrolyte.
  • the average value of the electrical conductivity is 10" 3 S/cm.
  • PVFM polyvinyl formal
  • NMP N-methylpyrrolidone
  • MDI diisocyanate
  • the mixed solution was coated with a film and immersed in deionized water to prepare a porous film, and the obtained porous film was dried for 1 hour.
  • the method of drying the porous film may be, for example, but not limited to, placing the porous film at 30 ° C - 60 ° C, by air drying or vacuum drying.
  • the high chemical stability of the PVFM polymer porous membrane prepared in Example 6, and the high liquid absorption rate of 45% promoted the formation of a stable gel electrolyte system.
  • the conductivity of the system was 1.12 X 10-S/cm, slightly higher than that of the liquid electrolyte.
  • the average conductivity is 103 ⁇ 4/cm.
  • polyvinyl acetal and polyvinyl butyral are used in the examples to prepare the polymer porous film of the present invention, those skilled in the art should be aware of polyvinyl formal and its homologues. All have the (1)-(4) basic structural unit as set forth in the description of the specification, the main structural features are similar, and both have certain hydroxyl groups, and the polyurethane of the polymer porous film of the present invention listed in the Summary of the Invention can be formed.
  • the chemical cross-linking structure can be used, and other homologues of polyvinyl formal can be used to prepare the polymer porous film of the present invention.
  • the organic solvent is preferably N-methylpyrrolidone, N,N-dimethylformamide, chloroform. At least one of tetrahydrofuran, an organic solvent having a solubility difference of ⁇ 1.7-2 in the field is also feasible.
  • MDI 4,4'-diphenylmethane diisocyanate
  • any other diisocyanate may be used to chemically crosslink with polyvinyl formal or a homolog thereof.
  • anhydrous methanol In addition to water, anhydrous methanol, anhydrous ethanol, such as a cheap and readily available non-solvent, it is also possible to add other polyvinyl formal or its homologue to a solution of polyvinyl formal or its homologue and diisocyanate.
  • a non-solvent for the polyurethaneized product The mass ratio of polyvinyl formal or its homologue to its organic solvent may be any ratio between 1:5 and 1:20.
  • the mass ratio of polyvinyl formal or its homologue to diisocyanate may be any ratio between 10:1 and 2:1.
  • the mass ratio of the polyethylol formal or its homologue to the non-solvent of the polyvinyl acetal and its chemically crosslinked product is any ratio between 10:1 and 1:1.
  • t ⁇ is lower than column 1
  • PVFM polyacetol formall
  • NMP N-methylpyrrolidone
  • the pellet was continuously magnetically stirred at 45 ° C until the precipitate was dissolved.
  • the solution was coated and immersed in deionized water to prepare a porous film, and the obtained porous film was dried for 1 hour.
  • Figure 4 is a microscopic topography of a porous polymer membrane.
  • the porous membrane has a porous honeycomb shape and has a large pore diameter of about 25 ⁇ m.
  • the polymer wall composed of large pores is also uniformly distributed, and the diameter is about 1-2 ⁇ m. Small pores.
  • the PVFM polymer porous film which is not chemically crosslinked is rapidly dissolved in an electrolyte containing an organic solvent such as LiPF 6 /EC+DMC (3:7 in Vol.), and a stable gel electrolyte system cannot be formed.
  • the composition of the polymer porous film of the present invention is chemically crosslinked, has good chemical stability, and the polymer porous film is not dissolved in the organic solvent component of the electrolytic solution.
  • the connected pores of the porous membrane can quickly adsorb the electrolyte and form a gel polymer electrolyte to effectively prevent the electrolyte from being missed.
  • the gel polymer electrolyte has high conductivity and reaches and approaches the average value of the liquid electrolyte conductivity of 1.12 ⁇ 10 ⁇ 3 .
  • the electrochemical stability window of the gel polymer electrolyte is 2.0V ⁇ 5.0V, and the result is shown in FIG. 5.
  • the impedance of the solution is 5.0 ⁇ through the AC impedance test, and the conductance is calculated according to the above formula.
  • the rate is 1.25 X 10- /cm.
  • the main components of the electrolytic solution used are a lithium salt and an organic solvent.
  • the lithium salt is selected from at least one of the following: LiPF 6 , LiC10 4 LiBF 4 , LiAsF 6 , LiAlCl 4 , LiCF 3 S ⁇ 3 , LiN(S0 2 CF 3 ) 2 , LiBOB, LiSbF 6 , LiSCN, LiSnF 6 , LiGeF 6 , LiTaF 6 .
  • the organic solvent is selected from at least one of the following: ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite Ester, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, ethyl acetate, ethyl propionate, ethyl butyrate, tetrahydrofuran, 2-methyl Tetrahydrofuran, tetrahydropyran, dioxolane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, acetonitrile, dimethyl sulfoxide, acetone, hydrazine, hydrazine-dimethylformamidine Amine, sulfolane, dimethyl sulfone.
  • the half cell is assembled with 1 ⁇ 1 ⁇ 2? ⁇ 4 as the positive electrode and Li as the negative electrode.
  • the battery uses a CR2032 button battery.
  • a separator member was not added to the battery, and instead, the polymer porous film prepared in Example 1 was used.
  • a small amount of electrolyte is added dropwise to infiltrate the polymer porous membrane and the electrode material, and the electrolyte is swollen to gel.
  • the polymer porous membrane prepared in Example 1 was applied to a gel polymer electrolyte, and a half-cell assembled using lithium iron phosphate as a positive electrode battery. After charging and discharging test, the results shown in FIG. 6 indicate that the embodiment was employed.
  • the prepared polymer porous membrane is applied to the gel polymer electrolyte with good chemical stability, excellent cycle stability of the battery, battery cycle 80 times, capacity retention rate of 95.4%, close to the liquid electrolyte cycle 80 times, capacity The application rate of 97.6% is maintained, and the application requirements in the battery system are achieved.
  • the polymer porous film prepared in Example 1 can also be used for a lithium ion battery in which positive and negative electrodes are composed of other materials.
  • the positive electrode of the lithium ion battery is at least one selected from the group consisting of lithium iron phosphate, nickel cobalt manganese ternary material, spinel lithium manganate, high capacity lithium-rich manganese-based material
  • the negative electrode is at least one selected from the group consisting of One: graphite, hard carbon, lithium niobate, silicon based compounds and alloys.
  • Fig. 1 shows an embodiment of a lithium ion battery cell structure obtained by using the polymer porous film of the present invention as a gel polymer electrolyte.
  • the lithium ion battery cell is a laminated type or a wound type, and includes a positive electrode tab 1, a positive electrode tab 2 welded to one end of the positive electrode tab 1, a negative electrode tab 3, and a sum welded to the negative electrode tab 3.
  • the negative electrode tab 4 at the same end of the positive electrode tab 2 and the gel polymer electrolyte layer 5 formed of the polymer porous film of the present invention between the positive and negative electrode tabs.
  • the lithium ion battery is deintercalated from the structure of the active material of the negative electrode tab 3 during discharge, and the active material of the negative electrode tab 3 is The solvation occurs at the interface of the gel polymer electrolyte layer 5, and migrates to the side of the positive electrode tab 1 in the gel polymer electrolyte layer 5, and the interface between the active material of the positive electrode tab 1 and the gel polymer electrolyte layer 5
  • the upper side is desolvated and then embedded in the structure of the material of the positive electrode tab 1, and the electrons are passed from the negative electrode tab 4 to the positive electrode tab 2 via an external circuit to form an directional movement of electrons, that is, an electric current.
  • lithium ions are deintercalated from the active material of the positive electrode tab 1 and traverse the interface between the gel polymer electrolyte layer 5 and the positive electrode tab 1 and the negative electrode tab 3, and then embedded in the negative electrode tab. 3
  • the structure of the active substance in the charging process, in contrast to the above process, lithium ions are deintercalated from the active material of the positive electrode tab 1 and traverse the interface between the gel polymer electrolyte layer 5 and the positive electrode tab 1 and the negative electrode tab 3, and then embedded in the negative electrode tab. 3 The structure of the active substance.
  • a gel polymer lithium ion battery for a gel polymer lithium ion battery, since a polymer porous film having a certain mechanical strength is used to adsorb-swell a gel polymer electrolyte formed after the electrolyte, the use of a separator is avoided. It reduces the multiple interfaces during lithium ion migration and the obstacles caused by the separator, which is more conducive to the migration of lithium ions and reduces the internal resistance of lithium ion batteries.
  • the shape of the battery is not limited by the liquid electrolyte, but it can be made according to the design requirements.

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Abstract

La présente invention concerne une membrane polymère poreuse obtenue par utilisation d'un polymère de polyvinylacétal traité au polyuréthane, et un procédé de préparation de ladite membrane polymère poreuse. Des pores traversants sont répartis uniformément dans la membrane poreuse, ce qui confère à ladite membrane d'excellentes capacités d'adsorption de liquide électrolytique et assure une vitesse d'adsorption de liquide de 300 % ou plus. L'adsorption et le gonflement du liquide électrolytique provoquent la gélification du système, et, la membrane poreuse et le système de gel peuvent ainsi rester stables pendant une longue période. L'électrolyte presque liquide de la présente invention présente une valeur de conductivité électrique moyenne de 1,0 x 10 -3 S/cm, une fenêtre de stabilité électrochimique comprise entre 2,0V et 5,0 V, des propriétés mécaniques et une électrocompatibilité nettement améliorées, et il peut servir d'électrolyte gel polymère, ce qui permet d'améliorer la sécurité de la batterie. L'invention rend inutile l'utilisation d'un système à électrolyte liquide ou d'un autre diaphragme de système de batterie en tant que support.
PCT/IB2013/002452 2012-11-09 2013-11-05 Membrane polymère poreuse, son procédé de préparation, et son utilisation dans un électrolyte gel polymère WO2014072789A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201210445230.X 2012-11-09
CN201210445230 2012-11-09
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EP3442070A1 (fr) * 2017-08-10 2019-02-13 Baden-Württemberg Stiftung gGmbH Électrolytes polymères en gel polyhydroxyurethane-based pour systèmes de stockage d'énergie
CN113140789A (zh) * 2021-04-22 2021-07-20 北京化工大学 一种可回收的自修复凝胶态电解质及其制备方法和应用
CN115133122A (zh) * 2022-08-29 2022-09-30 江苏展鸣新能源有限公司 一种锂离子电池电解质的制备方法及其应用
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EP3442070A1 (fr) * 2017-08-10 2019-02-13 Baden-Württemberg Stiftung gGmbH Électrolytes polymères en gel polyhydroxyurethane-based pour systèmes de stockage d'énergie
CN113140789A (zh) * 2021-04-22 2021-07-20 北京化工大学 一种可回收的自修复凝胶态电解质及其制备方法和应用
CN113140789B (zh) * 2021-04-22 2022-09-09 北京化工大学 一种可回收的自修复凝胶态电解质及其制备方法和应用
CN115133122A (zh) * 2022-08-29 2022-09-30 江苏展鸣新能源有限公司 一种锂离子电池电解质的制备方法及其应用
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CN118336151A (zh) * 2024-06-12 2024-07-12 超威电源集团有限公司 一种自愈合水系凝胶电池及其制备方法

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