WO2023159823A1 - Porous fiber composite separator and preparation method therefor - Google Patents

Porous fiber composite separator and preparation method therefor Download PDF

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Publication number
WO2023159823A1
WO2023159823A1 PCT/CN2022/100731 CN2022100731W WO2023159823A1 WO 2023159823 A1 WO2023159823 A1 WO 2023159823A1 CN 2022100731 W CN2022100731 W CN 2022100731W WO 2023159823 A1 WO2023159823 A1 WO 2023159823A1
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solvent
fiber composite
functional
porous fiber
resin
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PCT/CN2022/100731
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French (fr)
Chinese (zh)
Inventor
庄志
杨登科
李堃
彭锟
宫晓明
王培勇
冶成良
程跃
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上海恩捷新材料科技有限公司
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Publication of WO2023159823A1 publication Critical patent/WO2023159823A1/en

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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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • 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
    • 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
    • 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
    • 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
    • H01M50/417—Polyolefins
    • 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
    • H01M50/44—Fibrous material
    • 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

Definitions

  • the invention belongs to the field of lithium battery diaphragms, in particular to a porous fiber composite diaphragm.
  • the lithium battery separator not only needs to effectively block the direct contact between the positive and negative electrodes of the battery, but also needs to have good ion conductivity to allow lithium ions to pass through quickly during charging and discharging.
  • the performance of the separator determines the interface structure and internal resistance of the lithium battery, which in turn affects the key characteristics of the battery such as capacity, cycle life, and charge-discharge current density. Therefore, the improvement of the performance of the separator plays an important role in improving the overall performance of the lithium-ion battery. effect.
  • the demand for separators with good ionic conductivity and high liquid absorption and retention has also been applied. Current studies have shown that increasing the porosity of the membrane can effectively improve the ionic conductivity and liquid absorption and retention performance of the membrane, but how to further improve the ionic conductivity of the porous membrane has become a new area of concern for technicians.
  • An object of the present invention is to provide a porous fiber composite diaphragm, which includes: a structural fiber formed by spinning a structural resin; and a functional fiber formed by spinning a functional resin, and the functional fiber
  • the fibers are interlinked and intertwined, wherein the functional fibers have carbonyl or cyano functional groups, and the structural resin contains polymethyl methacrylate, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalic acid Any one or more of glycol esters, polyurethanes, and polyesters.
  • the functional resin includes any one or more of polyacrylonitrile, polyarylether sulfone ketone, polypropylene oxide, polylactic acid, carboxymethyl cellulose, and polyacrylamide.
  • Another object of the present invention is to provide a method for preparing a porous fiber composite diaphragm, the method comprising: a first solution preparation step: uniformly mixing the structural resin, a first solvent and a second solvent to prepare a first solution solution; the second solution preparation step: uniformly mix the functional resin, a third solvent and the second solvent to prepare a second solution; spinning step: load the first solution with a first syringe, and use the second Two syringes are installed in the second solution, spraying the first solution at a first feed rate to form the structural fibers and spraying the second solution at a second feed rate to form the function in an electrostatic field, respectively Fiber; film forming step: the structural fiber and the functional fiber are cross-linked and intertwined on a substrate to form the porous fiber composite membrane.
  • the speed ratio of the first feed rate to the second feed rate is 1:1 to 1:5.
  • said first feed rate is between 0.1 ml/h and 10.0 ml/h; said second feed rate is between 0.1 ml/h and 10.0 ml/h.
  • the electrostatic field is formed by a voltage between 5.0 kV and 20.0 kV.
  • the first injector or the second injector is spaced from the substrate by a specific feeding distance, and the feeding distance is between 100 mm and 200 mm.
  • the first solvent includes one of dimethylsulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexafluoropropanol. one or more; the second solvent includes one or more of ethanol, propanol, dimethyl carbonate; preferably, the structural resin: the first solvent: the second solvent For (0.5g to 2.0g): (5.0ml to 9.0ml): (1.0ml to 5.0ml).
  • the third solvent includes one of dimethylsulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexafluoropropanol. one or more; the fourth solvent includes one or more of ethanol, propanol, and methylene chloride dimethyl carbonate; preferably, the functional resin: the first solvent: the second solvent For (0.5g to 2.0g): (5.0ml to 9.0ml): (1.0ml to 5.0ml).
  • the structural resin is polymethyl methacrylate and the functional resin is polyacrylonitrile.
  • the first solvent is dimethylsulfoxide
  • the second solvent is dichloromethane
  • the third solvent is tetrahydrofuran
  • the fourth solvent is dichloromethane
  • the preparation method further includes: a heat treatment step: collecting the porous fiber composite diaphragm from the base material and placing it on a substrate, and heat treating the porous fiber composite diaphragm at a temperature.
  • the substrate includes a glass plate or a plastic plate.
  • the temperature is between 100°C and 150°C.
  • solutions are respectively prepared with functional resins containing carbonyl or cyano functional groups and structural resins with high mechanical strength, and the prepared solutions are respectively added to the electrospinning equipment.
  • Different spinning nozzles are used to spin at the same time; under the interference of the electrostatic field between different nozzles, in the process of spinning to form functional fibers and structural fibers, the two are entangled with each other, so that the two fibers are evenly distributed and alternate. The intertwined fibers are subsequently formed into a membrane.
  • the beneficial effect obtained by the above method of the present invention is: the two kinds of resin fibers are cross-linked and entangled during the spinning process, forming a large number of pore structures, so that the finished diaphragm at the rear end has good wetting performance and liquid absorption and liquid retention performance;
  • the cross-linking of the structural resin and the functional resin makes the porous fiber composite separator have good tensile strength, and the carbonyl or cyano group in the functional resin can interact with the solvent molecules in the electrolyte to improve the wettability of the separator to the electrolyte. Reducing the interface resistance can also enhance the ion conductivity, which is conducive to the rapid passage of lithium ions through the separator during charging and discharging, reducing the loss of lithium ions, and effectively improving the cycle performance and rate performance of lithium batteries.
  • One embodiment of the present invention is a porous fiber composite diaphragm, which includes: a structural fiber, formed by spinning a structural resin; and a functional fiber, formed by spinning a functional resin, and the functional fiber
  • the fibers are interlinked and intertwined, wherein the functional fibers have carbonyl or cyano functional groups.
  • the structural resin comprises polymethyl methacrylate (Poly (methyl methacrylate), PMMA), polystyrene (Polystyrene, PS), polyvinylidene difluoride (Polyvinylidene difluoride, PVDF), polytetrafluoroethylene (Polytetrafluoroethylene , PTFE), polyethylene terephthalate (Polyethylene terephthalate, PET), polyurethane (Polyurethane, PUR), polyester (Polyester, PE) in any one or more; More preferably, described structure
  • the resin is polymethyl methacrylate.
  • the functional resin comprises polyacrylonitrile (Polyacrylonitrite, PAN), polyarylether sulfone ketone (polyetheretherketon, PEEK), polypropylene oxide (Poly[oxy(methyl-1,2-ethanediyl)]), polylactic acid (Polylactic Acid, PLA), carboxymethyl cellulose (Carboxymethyl Cellulose, CMC), polyacrylamide (polyacrylamide, PAM) any one or more; More preferably, described functional resin is polyacrylonitrile.
  • PAN polyacrylonitrite
  • PEEK polyarylether sulfone ketone
  • PEEK polypropylene oxide
  • Poly[oxy(methyl-1,2-ethanediyl)] Polylactic acid
  • PLA Polylactic Acid
  • CMC Carboxymethyl Cellulose
  • PAM polyacrylamide
  • the carbonyl or cyano group contained in the functional resin can inhibit the anion from penetrating the separator in back-end applications; for example, when the electrolyte contains carbonate, the carbonyl or cyano group can dissolve the carbonate
  • the intermolecular interactions repel negatively charged carbonate anions, thereby inhibiting the ability of carbonate anions to pass through the separator, increasing the migration rate of cations, and enhancing the wettability of the separator to the electrolyte.
  • Another embodiment of the present invention is a preparation method of a porous fiber composite diaphragm, used to prepare the aforementioned porous fiber composite diaphragm; please refer to Figure 1, the preparation method includes:
  • Step of preparing the first solution uniformly mixing the structural resin, a first solvent and a second solvent to prepare a first solution;
  • S3) spinning step loading the first solution with a first syringe, loading the second solution with a second syringe, spraying the first solution at a first feed rate in an electrostatic field respectively to form the said structural fibers and spraying said second solution at a second feed rate to form said functional fibers;
  • the speed ratio of the first feed rate to the second feed rate is 1:1 to 1:5.
  • said first feed rate is between 0.1 ml/h and 10.0 ml/h; said second feed rate is between 0.1 ml/h and 10.0 ml/h.
  • the electrostatic field is formed by a voltage between 5.0 kV and 20.0 kV.
  • the feeding distance (L) is between 100mm and 200mm between.
  • the electrospinning method is implemented in the spinning step, and the spinning device (1) used can be listed as a receiving roll (13) with double injectors, and the double injectors can be along the long axis of the receiving roll ( The mode that Ax) direction moves left and right carries out spinning;
  • Fig. 2 is the schematic diagram of an exemplary spinning device (1), and in this example, spinning device (1) comprises the first injector (11), the second The syringe (12) and the receiving roller (13), specifically, contain the first solution (A) in the first syringe (11), and the second solution B in the second syringe (12), and are respectively set to the first solution (A).
  • the feed rate and the second feed rate are transmitted toward the receiving roller (13) to form structural fibers (A1) and functional fibers (B1) respectively, and the receiving roller (13) rotates 360 degrees with the major axis Ax as the axis, and the structural fibers (A1 ) and functional fibers (B1) are cross-linked and wound in the feeding space (Sp) and gradually attached to the receiving roller; further, the first injector (11) and the second injector (12) move left and right along the receiving roller, which can Make the structural fiber (A1) and the functional fiber (B1) cross-linked and entwined more uniformly, so that the pore distribution of the porous fiber composite diaphragm produced later is more uniform; please refer to Figure 3 again, which is an exemplary spinning device 2 In this example, the difference from the spinning device (1) is that the first injector 21 and the second injector 22 are relatively arranged on both sides of the long axis (Ax) of the receiving roll; The left and right movement modes of the first syringe (11) and the second s
  • the substrate may be formed of glass or plastic; preferably, the substrate is covered with a metal layer, and the metal layer is more preferably aluminum foil.
  • the first solvent includes dimethyl sulfoxide (Dimethyl sulfoxide, DMSO), tetrahydrofuran (Tetrahydrofuran, THF), N,N-dimethylformamide (Dimethylformamide, DMF), N,N-dimethyl One or more of acetamide (Dimethylacetamide, DMAc), N-methylpyrrolidone (N-Methyl-2-pyrrolidone, NMP), hexafluoropropanol (Hexafluoroisopropanol, HFIP);
  • the second solvent includes ethanol ( One or more in Ethanol, EtOH), propanol (Propanol, PrOH), dichloromethane (Methylene chloride, DCM), dimethyl carbonate;
  • described structural resin described first solvent: described The preparation ratio of the second solvent is (0.5g to 2.0g):(5.0ml to 9.0ml):(1.0ml to 5.0ml), more preferably 0.5
  • the third solvent includes one of dimethylsulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexafluoropropanol. one or more; the fourth solvent includes one or more of ethanol, propanol, and dimethyl carbonate; preferably, the functional resin: the third solvent: the fourth solvent (0.5g to 2.0g): (5.0ml to 9.0ml): (1.0ml to 5.0ml); preferably, the preparation ratio of the structural resin: the first solvent: the second solvent is 0.5g :8.0ml:2.0ml, more preferably 0.5g:8.0ml:2.0ml.
  • the preparation method further includes:
  • the substrate may be a glass or plastic plate.
  • the temperature ranges from 100°C to 150°C, more preferably 120°C; there is no special limitation on the drying environment or device, as long as it can control the ambient temperature within the temperature range, it can be used to dry porous Fiber composite membrane, such as heating and drying devices such as ovens and ovens.
  • Electrospinning Use two clean syringes to absorb the structural resin solution and the functional resin solution respectively; adjust the positive and negative high-voltage power supply to the range of 5.0kV to 20.0kV, and adjust the feeding distance between the syringe and the receiving roller to 100mm to 200mm interval; the surface of the aforementioned receiving roller is covered with a layer of aluminum foil; set the feeding rate of the syringe and start to pressure-feed the structural resin solution and the functional resin solution for electrospinning, and the feeding rate ratio is 1:1; under the action of the electric field, the structural resin solution and functional resin solution to form structural fibers and functional fibers respectively;
  • the ratio of PMMA: dimethyl sulfoxide: dichloromethane is 1.0g: 8.0ml: 2.0ml;
  • PAN Tetrahydrofuran: Dichloromethane The preparation ratio is 1.0g: 8.0ml: 2.0ml;
  • the feed rate ratio is 1:5.
  • the preparation ratio of PMMA: dimethyl sulfoxide: dichloromethane is 2.0g: 8.0ml: 2.0ml;
  • PAN Tetrahydrofuran: Dichloromethane The preparation ratio is 2.0g: 8.0ml: 2.0ml;
  • the feed rate ratio is 1:5.
  • Example 2 The steps are the same as in Example 1, except that both syringes draw the functional resin solution for spinning to obtain a porous fiber membrane.
  • m 1 is the mass of the sample before immersion
  • m 2 is the mass of the sample after immersion
  • the selected solvent is n-butanol
  • V 0 is the apparent volume of the diaphragm.
  • the solvent is n-butanol, and the quality difference of the diaphragm before and after immersion is used for determination.
  • the specific formula is as follows:
  • A% is the liquid absorption rate of the diaphragm
  • m1 is the mass of the sample before immersion
  • m2 is the mass of the sample after immersion.
  • the equipment is tested by Shanghai Xiangjie XJ8108C tensile machine.
  • the obtained composite film was cut into small discs with a diameter of 19 mm by a punching machine, assembled into a battery in a glove box, and electrochemically tested to measure the ionic conductivity.
  • the equipment used was the Zennium electrochemical workstation of ZAHNER in Germany, and the frequency range of the measurement was 0.01Hz to 100KHz, the amplitude is 0.001V.
  • Example 1 was compared with Comparative Example 1 and Comparative Example 2, unexpected technical effects were produced; under the expectation of addition, it was implemented with the feed rate ratio of 1:1, and Example 1
  • the technical effects obtained can be estimated as the average value achieved in Comparative Example 1 and Comparative Example 2, which are porosity porosity 69.5%, liquid absorption rate 430%, liquid retention rate 47.65%, tensile strength 50.0MPa, ion
  • the electrical conductivity is 2.50mS/cm; yet, the technical effects actually harvested in Example 1 are significantly greater than the expected effects, respectively reaching 77.0% porosity, 465% liquid absorption, 62.5% liquid retention, 73.0% tensile strength and
  • the ion conductivity is 3.30mS/cm; obviously, under the cross-linking and entanglement of the structural resin fiber and the functional resin fiber, there is a synergistic effect between them, which significantly improves the functionality of the porous fiber composite membrane, especially the ion conductivity
  • the improvement of the rate is the
  • the porous fiber composite diaphragm provided by the present invention and the preparation method thereof are respectively configured with a structural resin with high mechanical strength and a functional resin containing carbonyl or cyano functional groups, and then through the electrospinning method, the The two are spun to generate structural fibers and functional fibers respectively, which are interlinked and intertwined, evenly distributed and produce a synergistic effect, so that the subsequent porous fiber composite diaphragm has several excellent functions:
  • the two resin fibers are cross-linked and intertwined during the spinning process, resulting in a large pore structure, which improves the wetting performance and liquid absorption and liquid retention performance of the rear-end finished diaphragm.
  • the cross-linking of the two resin fibers makes the separator have good tensile strength, which is more reliable in the packaging of the battery liquid, and avoids the risk of battery liquid leakage during use.
  • the carbonyl or cyano group in the functional resin can interact with the solvent molecules in the electrolyte during the charging and discharging process, which further improves the wettability of the separator to the electrolyte, thereby reducing the interface resistance and enhancing the ionic strength.
  • the conductivity is conducive to the rapid passage of lithium ions through the separator, reducing the loss of lithium ions, and can effectively improve the cycle performance and rate performance of lithium batteries.

Abstract

A porous fiber composite separator, comprising: a structural fiber, formed by spinning of a structural resin; and a functional fiber, formed by spinning of a functional resin, and cross-linked and wound with the functional fiber. The functional fiber has a carbonyl or cyano functional group. The structural resin comprises any one or more of polymethyl methacrylate, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polyurethane, and polyester.

Description

一种多孔纤维复合隔膜及其制备方法A kind of porous fiber composite diaphragm and preparation method thereof 技术领域technical field
本发明属于锂电池隔膜领域，具体涉及一种多孔纤维复合隔膜。The invention belongs to the field of lithium battery diaphragms, in particular to a porous fiber composite diaphragm.
背景技术Background technique
锂电池隔膜作为四大关键材料之一，不仅需要有效阻隔电池正负极的直接接触，还需具备良好的离子导电能力，允许充放电时锂离子快速通过。隔膜性能的优劣决定了锂电池的界面结构和内阻，进而影响着电池的容量和循环寿命、充放电电流密度等关键特性，因此隔膜性能的提高对于提高锂离子电池的综合性能起着重要作用。随着市场对锂电池能量密度以及倍率性能提升不断提出新要求，对兼具良好离子导电率和高吸液保液性的隔膜的需求也应用而生。目前研究表明提高隔膜的孔隙率能有效提升隔膜的离子电导率和吸液保液性能，但如何进一步提高多孔隔膜的离子电导率则成为了备受技术人员关注的新领域。As one of the four key materials, the lithium battery separator not only needs to effectively block the direct contact between the positive and negative electrodes of the battery, but also needs to have good ion conductivity to allow lithium ions to pass through quickly during charging and discharging. The performance of the separator determines the interface structure and internal resistance of the lithium battery, which in turn affects the key characteristics of the battery such as capacity, cycle life, and charge-discharge current density. Therefore, the improvement of the performance of the separator plays an important role in improving the overall performance of the lithium-ion battery. effect. As the market continues to put forward new requirements for the energy density and rate performance of lithium batteries, the demand for separators with good ionic conductivity and high liquid absorption and retention has also been applied. Current studies have shown that increasing the porosity of the membrane can effectively improve the ionic conductivity and liquid absorption and retention performance of the membrane, but how to further improve the ionic conductivity of the porous membrane has become a new area of concern for technicians.
发明内容Contents of the invention
本发明之一目的在于提供一种多孔纤维复合隔膜，其包括：一结构纤维，是由一结构树脂纺丝所形成；及一功能纤维，是由一功能树脂纺丝所形成，与所述功能纤维相互交联缠绕，其中，所述功能纤维具有羰基或氰基官能团，所述结构树脂包含聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、聚四氟乙烯、聚对苯二甲酸乙二醇酯、聚氨酯、聚酯中的任意一种或多种。An object of the present invention is to provide a porous fiber composite diaphragm, which includes: a structural fiber formed by spinning a structural resin; and a functional fiber formed by spinning a functional resin, and the functional fiber The fibers are interlinked and intertwined, wherein the functional fibers have carbonyl or cyano functional groups, and the structural resin contains polymethyl methacrylate, polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalic acid Any one or more of glycol esters, polyurethanes, and polyesters.
如上所述之多孔纤维复合隔膜，所述功能树脂包含聚丙烯腈、聚芳醚砜酮、聚环氧丙烷、聚乳酸、羧甲基纤维素、聚丙烯酰胺中的任意一种或多种。In the porous fiber composite diaphragm as described above, the functional resin includes any one or more of polyacrylonitrile, polyarylether sulfone ketone, polypropylene oxide, polylactic acid, carboxymethyl cellulose, and polyacrylamide.
本发明之另一目的在于提供一种多孔纤维复合隔膜的制备方法，所述方法包括：第一溶液配制步骤：均匀混合所述结构树脂、一第一溶剂及一第二溶剂以配制成一 第一溶液；第二溶液配制步骤：均匀混合所述功能树脂、一第三溶剂及所述第二溶剂以配制成一第二溶液；纺丝步骤：以一第一注射器装载所述第一溶液，以第二注射器装在所述第二溶液，于一静电场中分别以第一馈送速率喷射所述第一溶液以形成所述结构纤维及以第二馈送速率喷射所述第二溶液以形成所述功能纤维；成膜步骤：所述结构纤维与所述功能纤维于一基材上互相交联缠绕以形成所述多孔纤维复合隔膜。Another object of the present invention is to provide a method for preparing a porous fiber composite diaphragm, the method comprising: a first solution preparation step: uniformly mixing the structural resin, a first solvent and a second solvent to prepare a first solution solution; the second solution preparation step: uniformly mix the functional resin, a third solvent and the second solvent to prepare a second solution; spinning step: load the first solution with a first syringe, and use the second Two syringes are installed in the second solution, spraying the first solution at a first feed rate to form the structural fibers and spraying the second solution at a second feed rate to form the function in an electrostatic field, respectively Fiber; film forming step: the structural fiber and the functional fiber are cross-linked and intertwined on a substrate to form the porous fiber composite membrane.
作为实例，所述第一馈送速率与所述第二馈送速率之速度比为1：1至1：5。As an example, the speed ratio of the first feed rate to the second feed rate is 1:1 to 1:5.
作为实例，所述第一馈送速率介于0.1ml/h至10.0ml/h之间；所述第二馈送速率介于0.1ml/h至10.0ml/h之间。As an example, said first feed rate is between 0.1 ml/h and 10.0 ml/h; said second feed rate is between 0.1 ml/h and 10.0 ml/h.
作为实例，所述静电场由5.0kV至20.0kV之间的电压所形成。As an example, the electrostatic field is formed by a voltage between 5.0 kV and 20.0 kV.
作为实例，所述第一注射器或所述第二注射器与所述基材之间间隔特定一馈送距离，所述馈送距离介于100mm至200mm之间。As an example, the first injector or the second injector is spaced from the substrate by a specific feeding distance, and the feeding distance is between 100 mm and 200 mm.
作为实例，所述第一溶剂包括二甲基亚砜、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、六氟丙醇中的一种或多种；所述第二溶剂包括乙醇、丙醇、二氯甲烷碳酸二甲酯中的一种或多种；优选地，所述结构树脂：所述第一溶剂：所述第二溶剂为(0.5g至2.0g):(5.0ml至9.0ml):(1.0ml至5.0ml)。As an example, the first solvent includes one of dimethylsulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexafluoropropanol. one or more; the second solvent includes one or more of ethanol, propanol, dimethyl carbonate; preferably, the structural resin: the first solvent: the second solvent For (0.5g to 2.0g): (5.0ml to 9.0ml): (1.0ml to 5.0ml).
作为实例，所述第三溶剂包括二甲基亚砜、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、六氟丙醇中的一种或多种；所述第四溶剂包括乙醇、丙醇、二氯甲烷碳酸二甲酯中的一种或多种；优选地，所述功能树脂：所述第一溶剂：所述第二溶剂为(0.5g至2.0g):(5.0ml至9.0ml):(1.0ml至5.0ml)。As an example, the third solvent includes one of dimethylsulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexafluoropropanol. one or more; the fourth solvent includes one or more of ethanol, propanol, and methylene chloride dimethyl carbonate; preferably, the functional resin: the first solvent: the second solvent For (0.5g to 2.0g): (5.0ml to 9.0ml): (1.0ml to 5.0ml).
作为实例，所述结构树脂是聚甲基丙烯酸甲酯，所述功能树脂是聚丙烯腈。As an example, the structural resin is polymethyl methacrylate and the functional resin is polyacrylonitrile.
作为实例，所述第一溶剂是二甲基亚砜，所述第二溶剂是二氯甲烷，所述第三 溶剂是四氢呋喃，所述第四溶剂是二氯甲烷。As an example, the first solvent is dimethylsulfoxide, the second solvent is dichloromethane, the third solvent is tetrahydrofuran, and the fourth solvent is dichloromethane.
进一步地，所述制备方法更包括：热处理步骤：自所述基材上收集所述多孔纤维复合隔膜并放置于一基板上，于一温度下热处理述多孔纤维复合隔膜。Further, the preparation method further includes: a heat treatment step: collecting the porous fiber composite diaphragm from the base material and placing it on a substrate, and heat treating the porous fiber composite diaphragm at a temperature.
作为实例，所述基板包括玻璃板或塑胶板。As an example, the substrate includes a glass plate or a plastic plate.
作为实例，所述温度介于100℃至150℃。As an example, the temperature is between 100°C and 150°C.
本发明所提供之多孔纤维复合隔膜及其制备方法，以含羰基或氰基官能团的功能树脂和机械强度较高的结构树脂分别配置溶液，并通过将配制之溶液分别加入静电纺丝设备所具备地不同纺丝喷头，以同时进行纺丝；在不同喷头之间地静电场干扰作用下，纺丝形成功能纤维及结构纤维地过程中，两者相互缠绕，使得两种纤维得均匀分布，交缠混杂的纤维后续制成隔膜。In the porous fiber composite diaphragm provided by the present invention and its preparation method, solutions are respectively prepared with functional resins containing carbonyl or cyano functional groups and structural resins with high mechanical strength, and the prepared solutions are respectively added to the electrospinning equipment. Different spinning nozzles are used to spin at the same time; under the interference of the electrostatic field between different nozzles, in the process of spinning to form functional fibers and structural fibers, the two are entangled with each other, so that the two fibers are evenly distributed and alternate. The intertwined fibers are subsequently formed into a membrane.
本发明通过前述方法所收获的有益效果是：两种树脂纤维在纺丝的过程中交联缠绕，形成了大量的孔隙结构，使得后端成品隔膜具备良好的浸润性能和吸液保液性能；此外，结构树脂和功能树脂的交联使得多孔纤维复合隔膜具备良好的拉伸强度，且功能树脂中的羰基或氰基可以和电解液中溶剂分子相互作用，提高隔膜对电解液的浸润性，减小介面电阻，更可以增强离子导电性，从而有利于充放电时锂离子快速通过隔膜，减少了锂离子损耗，有效提升了锂电池的循环性能和倍率性能。The beneficial effect obtained by the above method of the present invention is: the two kinds of resin fibers are cross-linked and entangled during the spinning process, forming a large number of pore structures, so that the finished diaphragm at the rear end has good wetting performance and liquid absorption and liquid retention performance; In addition, the cross-linking of the structural resin and the functional resin makes the porous fiber composite separator have good tensile strength, and the carbonyl or cyano group in the functional resin can interact with the solvent molecules in the electrolyte to improve the wettability of the separator to the electrolyte. Reducing the interface resistance can also enhance the ion conductivity, which is conducive to the rapid passage of lithium ions through the separator during charging and discharging, reducing the loss of lithium ions, and effectively improving the cycle performance and rate performance of lithium batteries.
具体实施方式Detailed ways
为进一步了解本发明，下面结合具体实施方式对本发明的优选方案进行描述，以利于本领域技术人员理解本发明。In order to further understand the present invention, the preferred solutions of the present invention will be described below in combination with specific embodiments, so as to facilitate those skilled in the art to understand the present invention.
本发明之一实施方式为一种多孔纤维复合隔膜，其包括：一结构纤维，是由一结构树脂纺丝所形成；及一功能纤维，是由一功能树脂纺丝所形成，与所述功能纤维相互交联缠绕，其中，所述功能纤维具有羰基或氰基官能团。One embodiment of the present invention is a porous fiber composite diaphragm, which includes: a structural fiber, formed by spinning a structural resin; and a functional fiber, formed by spinning a functional resin, and the functional fiber The fibers are interlinked and intertwined, wherein the functional fibers have carbonyl or cyano functional groups.
优选地，所述结构树脂包含聚甲基丙烯酸甲酯(Poly(methyl methacrylate)，PMMA)、聚苯乙烯(Polystyrene，PS)、聚偏氟乙烯(Polyvinylidene difluoride，PVDF)、聚四氟乙烯(Polytetrafluoroethylene，PTFE)、聚对苯二甲酸乙二醇酯(Polyethylene terephthalate，PET)、聚氨酯(Polyurethane，PUR)、聚酯(Polyester，PE)中的任意一种或多种；进一步优选地，所述结构树脂是聚甲基丙烯酸甲酯。Preferably, the structural resin comprises polymethyl methacrylate (Poly (methyl methacrylate), PMMA), polystyrene (Polystyrene, PS), polyvinylidene difluoride (Polyvinylidene difluoride, PVDF), polytetrafluoroethylene (Polytetrafluoroethylene , PTFE), polyethylene terephthalate (Polyethylene terephthalate, PET), polyurethane (Polyurethane, PUR), polyester (Polyester, PE) in any one or more; More preferably, described structure The resin is polymethyl methacrylate.
优选地，所述功能树脂包含聚丙烯腈(Polyacrylonitrite,PAN)、聚芳醚砜酮(polyetheretherketon，PEEK)、聚环氧丙烷(Poly[oxy(methyl-1,2-ethanediyl)])、聚乳酸(Polylactic Acid，PLA)、羧甲基纤维素(Carboxymethyl Cellulose，CMC)、聚丙烯酰胺(polyacrylamide，PAM)中的任意一种或多种；进一步优选地，所述功能树脂是聚丙烯腈。Preferably, the functional resin comprises polyacrylonitrile (Polyacrylonitrite, PAN), polyarylether sulfone ketone (polyetheretherketon, PEEK), polypropylene oxide (Poly[oxy(methyl-1,2-ethanediyl)]), polylactic acid (Polylactic Acid, PLA), carboxymethyl cellulose (Carboxymethyl Cellulose, CMC), polyacrylamide (polyacrylamide, PAM) any one or more; More preferably, described functional resin is polyacrylonitrile.
具体而言，功能树脂中所含的羰基或氰基，在后端应用中可抑制阴离子穿透隔膜；举例来说，当电解液中含有碳酸盐，羰基或氰基可以和碳酸盐溶剂分子间相互作用以排斥带负电荷的碳酸盐阴离子，从而抑制了碳酸盐阴离子穿过隔膜的能力，提高阳离子的迁移速率，增进隔膜对电解液的浸润性。Specifically, the carbonyl or cyano group contained in the functional resin can inhibit the anion from penetrating the separator in back-end applications; for example, when the electrolyte contains carbonate, the carbonyl or cyano group can dissolve the carbonate The intermolecular interactions repel negatively charged carbonate anions, thereby inhibiting the ability of carbonate anions to pass through the separator, increasing the migration rate of cations, and enhancing the wettability of the separator to the electrolyte.
本发明之另一实施方式是一种多孔纤维复合隔膜的制备方法，用以制备前述多孔纤维复合隔膜；请参阅图1，所述制备方法包括：Another embodiment of the present invention is a preparation method of a porous fiber composite diaphragm, used to prepare the aforementioned porous fiber composite diaphragm; please refer to Figure 1, the preparation method includes:
S1)第一溶液配制步骤：均匀混合所述结构树脂、一第一溶剂及一第二溶剂以配制成一第一溶液；S1) Step of preparing the first solution: uniformly mixing the structural resin, a first solvent and a second solvent to prepare a first solution;
S2)第二溶液配制步骤：均匀混合所述功能树脂、一第三溶剂及一第四溶剂以配制成一第二溶液；S2) second solution preparation step: uniformly mixing the functional resin, a third solvent and a fourth solvent to prepare a second solution;
S3)纺丝步骤：以一第一注射器装载所述第一溶液，以第二注射器装在所述第二溶液，于一静电场中分别以第一馈送速率喷射所述第一溶液以形成所述结构纤维 及以第二馈送速率喷射所述第二溶液以形成所述功能纤维；S3) spinning step: loading the first solution with a first syringe, loading the second solution with a second syringe, spraying the first solution at a first feed rate in an electrostatic field respectively to form the said structural fibers and spraying said second solution at a second feed rate to form said functional fibers;
S4)成膜步骤：所述结构纤维与所述功能纤维于一基材上互相交联缠绕以形成所述多孔纤维复合隔膜。S4) Membrane forming step: the structural fibers and the functional fibers are cross-linked and intertwined on a substrate to form the porous fiber composite membrane.
作为实例，所述第一馈送速率与所述第二馈送速率之速度比为1：1至1：5。As an example, the speed ratio of the first feed rate to the second feed rate is 1:1 to 1:5.
作为实例，所述第一馈送速率介于0.1ml/h至10.0ml/h之间；所述第二馈送速率介于0.1ml/h至10.0ml/h之间。As an example, said first feed rate is between 0.1 ml/h and 10.0 ml/h; said second feed rate is between 0.1 ml/h and 10.0 ml/h.
作为实例，所述静电场由5.0kV至20.0kV之间的电压所形成。As an example, the electrostatic field is formed by a voltage between 5.0 kV and 20.0 kV.
作为实例，所述纺丝步骤中，所述第一注射器或所述第二注射器与所述基材之间具有特定一馈送距离(L)，所述馈送距离(L)介于100mm至200mm之间。As an example, in the spinning step, there is a specific feeding distance (L) between the first syringe or the second syringe and the substrate, and the feeding distance (L) is between 100mm and 200mm between.
举例来说，于纺丝步骤中是实施以静电纺丝方法，其采用的纺丝装置(1)可列举以接收辊(13)搭配双注射器，而双注射器又可以是沿接收辊长轴(Ax)方向左右移动之方式进行纺丝；请参阅图2，是一示例性纺丝装置(1)之示意图，于此示例中，纺丝装置(1)包含第一注射器(11)、第二注射器(12)及接收辊(13)，具体来说，于第一注射器(11)盛装第一溶液(A)，于第二注射器(12)盛装第二溶液B，并分别设定以第一馈送速率及第二馈送速率朝接收辊(13)发射以分别形成结构纤维(A1)及功能纤维(B1)，接收辊(13)以长轴Ax为轴心进行360度旋转，结构纤维(A1)及功能纤维(B1)在馈送空间(Sp)中交联缠绕并逐渐贴附于接收辊上；进一步地，通过第一注射器(11)与第二注射器(12)沿接收辊左右移动，可更加均匀的令结构纤维(A1)及功能纤维(B1)交联缠绕，以使后续产生的多孔纤维复合隔膜其孔隙分布更加均匀；再请参阅图3，是说明令一示例性纺丝装置2之示意图，于此示例中，与纺丝装置(1)不同的地方在于，第一注射器21与第二注射器22是相对设置于接收辊长轴(Ax)的两侧平面上；再者，第一注射器(11)与第二注射器(12)的左右移动模式可以是同步左 右移动，也可以是交错左右移动，其模式并没有特别限制；注射器的喷嘴可以加装针头，也可以在无针头的状态下进行纺丝。For example, the electrospinning method is implemented in the spinning step, and the spinning device (1) used can be listed as a receiving roll (13) with double injectors, and the double injectors can be along the long axis of the receiving roll ( The mode that Ax) direction moves left and right carries out spinning; Please refer to Fig. 2, is the schematic diagram of an exemplary spinning device (1), and in this example, spinning device (1) comprises the first injector (11), the second The syringe (12) and the receiving roller (13), specifically, contain the first solution (A) in the first syringe (11), and the second solution B in the second syringe (12), and are respectively set to the first solution (A). The feed rate and the second feed rate are transmitted toward the receiving roller (13) to form structural fibers (A1) and functional fibers (B1) respectively, and the receiving roller (13) rotates 360 degrees with the major axis Ax as the axis, and the structural fibers (A1 ) and functional fibers (B1) are cross-linked and wound in the feeding space (Sp) and gradually attached to the receiving roller; further, the first injector (11) and the second injector (12) move left and right along the receiving roller, which can Make the structural fiber (A1) and the functional fiber (B1) cross-linked and entwined more uniformly, so that the pore distribution of the porous fiber composite diaphragm produced later is more uniform; please refer to Figure 3 again, which is an exemplary spinning device 2 In this example, the difference from the spinning device (1) is that the first injector 21 and the second injector 22 are relatively arranged on both sides of the long axis (Ax) of the receiving roll; The left and right movement modes of the first syringe (11) and the second syringe (12) can be synchronous left and right movement, or staggered left and right movement, and the mode is not particularly limited; state for spinning.
作为实例，所述基材可以由玻璃或塑胶所形成；优选地，并所述基材覆盖有一金属层，所述金属层进一步优选铝箔。As an example, the substrate may be formed of glass or plastic; preferably, the substrate is covered with a metal layer, and the metal layer is more preferably aluminum foil.
作为实例，所述第一溶剂包括二甲基亚砜(Dimethyl sulfoxide，DMSO)、四氢呋喃(Tetrahydrofuran，THF)、N,N-二甲基甲酰胺(Dimethylformamide，DMF)、N,N-二甲基乙酰胺(Dimethylacetamide，DMAc)、N-甲基吡咯烷酮(N-Methyl-2-pyrrolidone，NMP)、六氟丙醇(Hexafluoroisopropanol，HFIP)中的一种或多种；所述第二溶剂包括乙醇(Ethanol,EtOH)、丙醇(Propanol，PrOH)、二氯甲烷(Methylene chloride，DCM)、碳酸二甲酯中的一种或多种；优选地，所述结构树脂：所述第一溶剂：所述第二溶剂之配制比例为(0.5g至2.0g):(5.0ml至9.0ml):(1.0ml至5.0ml)，进一步优选0.5g:8.0ml:2.0ml。As an example, the first solvent includes dimethyl sulfoxide (Dimethyl sulfoxide, DMSO), tetrahydrofuran (Tetrahydrofuran, THF), N,N-dimethylformamide (Dimethylformamide, DMF), N,N-dimethyl One or more of acetamide (Dimethylacetamide, DMAc), N-methylpyrrolidone (N-Methyl-2-pyrrolidone, NMP), hexafluoropropanol (Hexafluoroisopropanol, HFIP); the second solvent includes ethanol ( One or more in Ethanol, EtOH), propanol (Propanol, PrOH), dichloromethane (Methylene chloride, DCM), dimethyl carbonate; Preferably, described structural resin: described first solvent: described The preparation ratio of the second solvent is (0.5g to 2.0g):(5.0ml to 9.0ml):(1.0ml to 5.0ml), more preferably 0.5g:8.0ml:2.0ml.
作为实例，所述第三溶剂包括二甲基亚砜、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、六氟丙醇中的一种或多种；所述第四溶剂包括乙醇、丙醇、二氯甲烷碳酸二甲酯中的一种或多种；优选地，所述功能树脂：所述第三溶剂：所述第四溶剂为(0.5g至2.0g):(5.0ml至9.0ml):(1.0ml至5.0ml)；优选地，所述结构树脂：所述第一溶剂：所述第二溶剂之配制比例为0.5g:8.0ml:2.0ml，进一步优选0.5g:8.0ml:2.0ml。As an example, the third solvent includes one of dimethylsulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and hexafluoropropanol. one or more; the fourth solvent includes one or more of ethanol, propanol, and dimethyl carbonate; preferably, the functional resin: the third solvent: the fourth solvent (0.5g to 2.0g): (5.0ml to 9.0ml): (1.0ml to 5.0ml); preferably, the preparation ratio of the structural resin: the first solvent: the second solvent is 0.5g :8.0ml:2.0ml, more preferably 0.5g:8.0ml:2.0ml.
作为一较佳实例，所述制备方法更包括：As a preferred example, the preparation method further includes:
S5)热处理步骤：自所述基材上收集所述多孔纤维复合隔膜并放置于一基板上，于一温度下热处理述多孔纤维复合隔膜。S5) heat treatment step: collecting the porous fiber composite membrane from the base material and placing it on a substrate, and heat treating the porous fiber composite membrane at a temperature.
作为实例，所述基板可以是玻璃板或塑胶板。As an example, the substrate may be a glass or plastic plate.
作为实例，所述温度介于100℃至150℃，进一步优选120℃；对于干燥的环境或装置并无特别限制，只要是可以将环境温度控制于所述温度区间的设备都可以用来干燥多孔纤维复合隔膜，例如烘箱、烤箱等加热干燥装置。As an example, the temperature ranges from 100°C to 150°C, more preferably 120°C; there is no special limitation on the drying environment or device, as long as it can control the ambient temperature within the temperature range, it can be used to dry porous Fiber composite membrane, such as heating and drying devices such as ovens and ovens.
下文将列举数个实施例进一步体现本发明所提供之多孔纤维复合隔膜及其制备方法所达到的其技术效果。Several examples will be enumerated below to further demonstrate the technical effects achieved by the porous fiber composite membrane and its preparation method provided by the present invention.
实施例1Example 1
1)结构树脂溶液配制：将PMMA树脂与二甲基亚砜及二氯甲烷之混合液配置成均一结构树脂溶液，其中PMMA：二甲基亚砜：二氯甲烷之配制比例为0.5g：8.0ml：2.0ml；1) Preparation of structural resin solution: The mixture of PMMA resin, dimethyl sulfoxide and dichloromethane is prepared into a uniform structural resin solution, wherein the preparation ratio of PMMA: dimethyl sulfoxide: dichloromethane is 0.5g: 8.0 ml: 2.0ml;
2)功能树脂溶液配制：将PAN树脂与四氢呋喃及二氯化碳之混合液配置成均一功能树脂液，其中PAN：四氢呋喃：二氯甲烷之配制比例为0.5g：8.0ml：2.0ml；2) Preparation of functional resin solution: prepare a mixture of PAN resin, tetrahydrofuran and carbon dichloride to form a uniform functional resin solution, wherein the preparation ratio of PAN: tetrahydrofuran: dichloromethane is 0.5g: 8.0ml: 2.0ml;
3)静电纺丝：以洁净的两只注射器分别吸取结构树脂溶液、功能树脂溶液；调节正负高压电源大小至5.0kV至20.0kV区间，并调整注射器与接收辊之间的馈送距离至100mm至200mm区间；前述接收辊表面覆盖有一层铝箔；设置注射器之馈送速率并开始压送结构树脂溶液及功能树脂溶液进行静电纺丝，其馈送速率比为1：1；在电场作用下，结构树脂溶液及功能树脂溶液分别抽丝形成结构纤维及功能纤维；3) Electrospinning: Use two clean syringes to absorb the structural resin solution and the functional resin solution respectively; adjust the positive and negative high-voltage power supply to the range of 5.0kV to 20.0kV, and adjust the feeding distance between the syringe and the receiving roller to 100mm to 200mm interval; the surface of the aforementioned receiving roller is covered with a layer of aluminum foil; set the feeding rate of the syringe and start to pressure-feed the structural resin solution and the functional resin solution for electrospinning, and the feeding rate ratio is 1:1; under the action of the electric field, the structural resin solution and functional resin solution to form structural fibers and functional fibers respectively;
4)成膜：结构纤维及功能纤维在接收辊表面铝箔上交联缠绕形成一层纤维膜；4) Film formation: structural fibers and functional fibers are cross-linked and wound on the aluminum foil on the surface of the receiving roller to form a layer of fiber film;
5)热处理：将纤维膜自铝箔上剥落，之后夹在玻璃板中间放入120℃烘箱热处理1小时，即得到多孔纤维复合隔膜。5) Heat treatment: The fiber membrane was peeled off from the aluminum foil, then sandwiched between glass plates and placed in an oven at 120°C for heat treatment for 1 hour to obtain a porous fiber composite separator.
实施例2Example 2
步骤同实施例1，差别在于馈送速率比为1：3。The steps are the same as in Example 1, except that the feeding rate ratio is 1:3.
实施例3Example 3
步骤同实施例1，差别在于馈送速率比为1：5。The steps are the same as in Example 1, the difference is that the feeding rate ratio is 1:5.
实施例4Example 4
步骤同实施例1，差别在于：Step is with embodiment 1, difference is:
PMMA：二甲基亚砜：二氯甲烷之配制比例为1.0g：8.0ml：2.0ml；The ratio of PMMA: dimethyl sulfoxide: dichloromethane is 1.0g: 8.0ml: 2.0ml;
PAN：四氢呋喃：二氯甲烷之配制比例为1.0g：8.0ml：2.0ml；PAN: Tetrahydrofuran: Dichloromethane The preparation ratio is 1.0g: 8.0ml: 2.0ml;
馈送速率比为1：5。The feed rate ratio is 1:5.
实施例5Example 5
步骤同实施例1，差别在于：Step is with embodiment 1, difference is:
PMMA：二甲基亚砜：二氯甲烷之配制比例为2.0g：8.0ml：2.0ml；The preparation ratio of PMMA: dimethyl sulfoxide: dichloromethane is 2.0g: 8.0ml: 2.0ml;
PAN：四氢呋喃：二氯甲烷之配制比例为2.0g：8.0ml：2.0ml；PAN: Tetrahydrofuran: Dichloromethane The preparation ratio is 2.0g: 8.0ml: 2.0ml;
馈送速率比为1：5。The feed rate ratio is 1:5.
对比例1Comparative example 1
步骤同实施例1，差别在于两只注射器均吸取结构树脂溶液进行纺丝以获得多孔纤维隔膜。The procedure is the same as that in Example 1, except that both syringes absorb the structural resin solution for spinning to obtain a porous fiber membrane.
对比例2Comparative example 2
步骤同实施例1，差别在于两只注射器均吸取功能树脂溶液进行纺丝以获得多孔纤维隔膜。The steps are the same as in Example 1, except that both syringes draw the functional resin solution for spinning to obtain a porous fiber membrane.
将上述实施例1至实施例5及对比例1、对比例2所得到的纤维隔膜之孔隙率、吸液率、保液率、拉伸强度、离子电导率等特性进行测试。The porosity, liquid absorption rate, liquid retention rate, tensile strength, ion conductivity and other properties of the fiber separator obtained in the above-mentioned Examples 1 to 5 and Comparative Example 1 and Comparative Example 2 were tested.
具体的测试方法说明如下：The specific test method is described as follows:
孔隙率测试Porosity test
通过测量隔膜浸润前后的质量差计算出隔膜被液体占据的空隙体积作为隔膜 的孔隙率，具体公式如下：Calculate the void volume of the diaphragm occupied by liquid by measuring the mass difference before and after the diaphragm is infiltrated as the porosity of the diaphragm. The specific formula is as follows:
Figure PCTCN2022100731-appb-000001
Figure PCTCN2022100731-appb-000001
其中m 1为浸泡前式样的质量，m 2为浸泡后式样的质量，选择溶剂为正丁醇，V 0为隔膜的表观体积。 Among them, m 1 is the mass of the sample before immersion, m 2 is the mass of the sample after immersion, the selected solvent is n-butanol, and V 0 is the apparent volume of the diaphragm.
吸液率测定Liquid Absorption Determination
采用溶剂为正丁醇，采用浸液前后隔膜的质量差进行测定，具体公式如下：The solvent is n-butanol, and the quality difference of the diaphragm before and after immersion is used for determination. The specific formula is as follows:
Figure PCTCN2022100731-appb-000002
Figure PCTCN2022100731-appb-000002
其中A％为隔膜吸液率，m 1为浸泡前试样的质量，m2为浸泡后试样的质量。 Among them, A% is the liquid absorption rate of the diaphragm, m1 is the mass of the sample before immersion, and m2 is the mass of the sample after immersion.
电解液吸液率和保液率Electrolyte liquid absorption rate and liquid retention rate
把得到的复合膜裁成2×2cm的试样烘干后称重，将称重后的干膜(W 0)浸泡在LiPF6电解液中,2h后取出,用滤纸擦净隔膜表面多余的电解液后称重得到湿膜的质量,记作W x1,饱和吸液后重量记作W 1；最后,浸润电解液的隔膜搁置在50℃烘箱中1小时后称量隔膜的质量,记作W x2；隔膜的吸液率及保液率的具体公式如下： Cut the obtained composite film into a sample of 2×2 cm, dry it and weigh it, soak the weighed dry film (W 0 ) in the LiPF6 electrolyte, take it out after 2 hours, and wipe off the excess electrolyte on the surface of the diaphragm with filter paper. The mass of the wet film is weighed after the solution is added, which is recorded as W x1 , and the weight after saturated liquid absorption is recorded as W 1 ; finally, the diaphragm soaked in the electrolyte is placed in an oven at 50°C for 1 hour, and the mass of the diaphragm is weighed, which is recorded as W x2 ; The specific formulas of the liquid absorption rate and liquid retention rate of the diaphragm are as follows:
Figure PCTCN2022100731-appb-000003
Figure PCTCN2022100731-appb-000003
Figure PCTCN2022100731-appb-000004
Figure PCTCN2022100731-appb-000004
拉伸强度测试Tensile Strength Test
设备采用上海湘杰XJ8108C拉伸机进行测试。The equipment is tested by Shanghai Xiangjie XJ8108C tensile machine.
电化学测试： Electrochemical test :
把得到的复合膜用冲孔机裁成直径19mm的小圆片，在手套箱中组装成电池，进行电化学测试测离子电导率，采用设备为德国ZAHNER的Zennium电化学工作站， 测量的频率范围为0.01Hz至100KHz，振幅为0.001V。The obtained composite film was cut into small discs with a diameter of 19 mm by a punching machine, assembled into a battery in a glove box, and electrochemically tested to measure the ionic conductivity. The equipment used was the Zennium electrochemical workstation of ZAHNER in Germany, and the frequency range of the measurement was 0.01Hz to 100KHz, the amplitude is 0.001V.
上述各项测试之结果列于表1；由1表可知，对比例1中单一组分的PMMA多孔纤维隔膜孔隙率不高，无法满足高的离子电导率要求，对比例2中单一组分的PAN多孔纤维隔膜虽然具有更高的孔隙率、吸液率，但是由于隔膜拉伸强度不高导致隔膜使用时漏液，保液率和离子电导不高，无法满足高的离子电导率要求。The results of the above-mentioned tests are listed in Table 1; as can be seen from Table 1, the porosity of the PMMA porous fiber membrane of a single component in Comparative Example 1 is not high, and cannot meet the high ion conductivity requirement. Although the PAN porous fiber membrane has higher porosity and liquid absorption rate, due to the low tensile strength of the membrane, the membrane leaks during use, the liquid retention rate and ion conductivity are not high, and cannot meet the high ion conductivity requirements.
再看到实施例1至实施例5，隔膜的拉伸强度除了随着PAN的含量增加而增加(56.0至69.0MPa)之外，在纺丝溶液中PMMA与PAN含量同步减小的条件下，隔膜的孔隙率(69.0至85.0％)、吸液率(320至501％)、保液率(66.4至73.8％)反而得到提升，其降低了隔膜内阻，从而提高了锂离子电池的离子电导率(2.94至3.66mS/cm)，使得电池在使用中具有更好的循环性能和充放电倍率。See again embodiment 1 to embodiment 5, except that the tensile strength of membrane increases (56.0 to 69.0MPa) along with the content of PAN, under the condition that PMMA and PAN content decrease synchronously in spinning solution, The porosity (69.0 to 85.0%), liquid absorption rate (320 to 501%), and liquid retention rate (66.4 to 73.8%) of the separator are improved instead, which reduces the internal resistance of the separator, thereby improving the ion conductivity of the lithium-ion battery Rate (2.94 to 3.66mS/cm), so that the battery has better cycle performance and charge-discharge rate in use.
表1Table 1
Figure PCTCN2022100731-appb-000005
Figure PCTCN2022100731-appb-000005
更具体地说，实施例1与对比例1、对比例2比较后，产生了预料之外的技术效果；在加成作用的预期下，以馈送速率比1:1的条件实施，实施例1所收获的技术效果可以预估为对比例1及对比例2所达成的平均值，分别为孔隙率孔隙率69.5％、 吸液率430％、保液率47.65％、拉伸强度50.0MPa、离子电导率2.50mS/cm；然而，实施例1实际收获的技术效果均显着地大于预期效果，分别达到了孔隙率77.0％、吸液率465％、保液率62.5％、拉伸强度73.0％以及离子导电率3.30mS/cm；显然地，在结构树脂纤维与功能树脂纤维的交联缠绕之下，其间发生了协同作用，从而显着的提升了多孔纤维复合隔膜的功能性，尤以离子导电率的提升最为显着，达到更好的循环性能与更高的充放电倍率。More specifically, after Example 1 was compared with Comparative Example 1 and Comparative Example 2, unexpected technical effects were produced; under the expectation of addition, it was implemented with the feed rate ratio of 1:1, and Example 1 The technical effects obtained can be estimated as the average value achieved in Comparative Example 1 and Comparative Example 2, which are porosity porosity 69.5%, liquid absorption rate 430%, liquid retention rate 47.65%, tensile strength 50.0MPa, ion The electrical conductivity is 2.50mS/cm; yet, the technical effects actually harvested in Example 1 are significantly greater than the expected effects, respectively reaching 77.0% porosity, 465% liquid absorption, 62.5% liquid retention, 73.0% tensile strength and The ion conductivity is 3.30mS/cm; obviously, under the cross-linking and entanglement of the structural resin fiber and the functional resin fiber, there is a synergistic effect between them, which significantly improves the functionality of the porous fiber composite membrane, especially the ion conductivity The improvement of the rate is the most significant, achieving better cycle performance and higher charge-discharge rate.
综上所评，本发明所提供之多孔纤维复合隔膜及其制备方法，以机械强度较高的结构树脂及含羰基或氰基官能团的功能树脂分别配置溶液，再通过将静电纺丝方法，使两者抽丝分别生成结构纤维与功能纤维，其相互交联缠绕、分布均匀并产生了协同效果，令后续制成的多孔纤维复合隔膜具有数种优异功能：To sum up, the porous fiber composite diaphragm provided by the present invention and the preparation method thereof are respectively configured with a structural resin with high mechanical strength and a functional resin containing carbonyl or cyano functional groups, and then through the electrospinning method, the The two are spun to generate structural fibers and functional fibers respectively, which are interlinked and intertwined, evenly distributed and produce a synergistic effect, so that the subsequent porous fiber composite diaphragm has several excellent functions:
其一，两种树脂纤维在纺丝过程中交联缠绕，产生了大量的孔隙结构，提升了后端成品隔膜的浸润性能和吸液保液性能。First, the two resin fibers are cross-linked and intertwined during the spinning process, resulting in a large pore structure, which improves the wetting performance and liquid absorption and liquid retention performance of the rear-end finished diaphragm.
其二，两种树脂纤维的交联使得隔膜具有良好的拉伸强度，在电池液的封装上更加牢靠，避免了使用中电池漏液的风险。Second, the cross-linking of the two resin fibers makes the separator have good tensile strength, which is more reliable in the packaging of the battery liquid, and avoids the risk of battery liquid leakage during use.
其三，功能树脂中所具备的羰基或氰基在充放电的过程中，可以和电解液中的溶剂分子相互作用，更加提升了隔膜对电解液的浸润性，从而减小介面电阻、增强离子导电性，有利于锂离子快速通过隔膜，降低锂离子损耗，可有效提升锂电池的循环性能和倍率性能。Third, the carbonyl or cyano group in the functional resin can interact with the solvent molecules in the electrolyte during the charging and discharging process, which further improves the wettability of the separator to the electrolyte, thereby reducing the interface resistance and enhancing the ionic strength. The conductivity is conducive to the rapid passage of lithium ions through the separator, reducing the loss of lithium ions, and can effectively improve the cycle performance and rate performance of lithium batteries.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明范围。The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, some improvements and modifications can also be made, and these improvements and modifications should also be considered For the scope of the present invention.

Claims (12)

  1. 一种多孔纤维复合隔膜，其包括：A porous fiber composite membrane comprising:
    一结构纤维，是由一结构树脂纺丝所形成；及a structural fiber formed by spinning a structural resin; and
    一功能纤维，是由一功能树脂纺丝所形成，与所述功能纤维相互交联缠绕，其中，所述功能纤维具有羰基或氰基官能团，所述结构树脂是包含聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯、聚四氟乙烯、聚对苯二甲酸乙二醇酯、聚氨酯、聚酯中的任意一种或多种。A functional fiber is formed by spinning a functional resin, cross-linked and entwined with the functional fiber, wherein the functional fiber has a carbonyl or cyano functional group, and the structural resin is composed of polymethyl methacrylate, Any one or more of polystyrene, polyvinylidene fluoride, polytetrafluoroethylene, polyethylene terephthalate, polyurethane, polyester.
  2. 如权利要求1所述之多孔纤维复合隔膜，其特征在于，所述功能树脂包含聚丙烯腈、聚芳醚砜酮、聚环氧丙烷、聚乳酸、羧甲基纤维素、聚丙烯酰胺中的任意一种或多种。The porous fiber composite membrane according to claim 1, wherein the functional resin comprises polyacrylonitrile, polyarylether sulfone ketone, polypropylene oxide, polylactic acid, carboxymethyl cellulose, polyacrylamide Any one or more.
  3. 如权利要求1或2所述之多孔纤维复合隔膜，其制备方法包括：The porous fiber composite diaphragm as claimed in claim 1 or 2, its preparation method comprises:
    第一溶液配制步骤：均匀混合所述结构树脂、一第一溶剂及一第二溶剂以配制成一第一溶液；The first solution preparation step: uniformly mixing the structural resin, a first solvent and a second solvent to prepare a first solution;
    第二溶液配制步骤：均匀混合所述功能树脂、一第三溶剂及一第四溶剂以配制成一第二溶液；The second solution preparation step: uniformly mixing the functional resin, a third solvent and a fourth solvent to prepare a second solution;
    纺丝步骤：以一第一注射器装载所述第一溶液，以第二注射器装在所述第二溶液，于一静电场中分别以第一馈送速率喷射所述第一溶液以形成所述结构纤维及以第二馈送速率喷射所述第二溶液以形成所述功能纤维；spinning step: loading the first solution with a first syringe, loading the second solution with a second syringe, spraying the first solution respectively at a first feed rate in an electrostatic field to form the structure fibers and spraying the second solution at a second feed rate to form the functional fibers;
    成膜步骤：所述结构纤维与所述功能纤维于一基材上互相交联缠绕以形成所述多孔纤维复合隔膜。Membrane forming step: the structural fibers and the functional fibers are interlinked and intertwined on a substrate to form the porous fiber composite membrane.
  4. 如权利要求3所述之多孔纤维复合隔膜，其特征在于，所述第一馈送速率与所述第二馈送速率之速度比为1：1至1：5。The porous fiber composite membrane according to claim 3, wherein the speed ratio of the first feed rate to the second feed rate is 1:1 to 1:5.
  5. 如权利要求3或4所述之多孔纤维复合隔膜，其特征在于，所述第一溶剂包 括二甲基亚砜、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、六氟丙醇中的一种或多种；所述第二溶剂包括乙醇、丙醇、二氯甲烷、碳酸二甲酯中的一种或多种。The porous fiber composite membrane according to claim 3 or 4, wherein the first solvent comprises dimethyl sulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide One or more of amides, N-methylpyrrolidone, and hexafluoropropanol; the second solvent includes one or more of ethanol, propanol, methylene chloride, and dimethyl carbonate.
  6. 如权利要求5所述之多孔纤维复合隔膜，其特征在于，所述第三溶剂包括二甲基亚砜、四氢呋喃、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、六氟丙醇中的一种或多种；所述第四溶剂包括乙醇、丙醇、二氯甲烷、碳酸二甲酯中的一种或多种。The porous fiber composite membrane according to claim 5, wherein the third solvent comprises dimethyl sulfoxide, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, One or more of N-methylpyrrolidone and hexafluoropropanol; the fourth solvent includes one or more of ethanol, propanol, methylene chloride, and dimethyl carbonate.
  7. 如权利要求6所述之多孔纤维复合隔膜，其特征在于，所述结构树脂为聚甲基丙烯酸甲酯，所述功能树脂为聚丙烯腈；所述第一溶剂为二甲基亚砜，所述第二溶剂为二氯甲烷；所述第三溶剂为四氢呋喃，所述第四溶剂为二氯甲烷。The porous fiber composite membrane according to claim 6, wherein the structural resin is polymethyl methacrylate, the functional resin is polyacrylonitrile; the first solvent is dimethyl sulfoxide, and the The second solvent is dichloromethane; the third solvent is tetrahydrofuran, and the fourth solvent is dichloromethane.
  8. 如权利要求6所述之多孔纤维复合隔膜，其特征在于，所述结构树脂：所述第一溶剂：所述第二溶剂为(0.5g至2.0g):(5.0ml至9.0ml):(1.0ml至5.0ml)。The porous fiber composite membrane according to claim 6, characterized in that, the structural resin: the first solvent: the second solvent is (0.5g to 2.0g): (5.0ml to 9.0ml): ( 1.0ml to 5.0ml).
  9. 如权利要求6所述之多孔纤维复合隔膜，其特征在于，所述功能树脂：所述第三溶剂：所述第四溶剂为(0.5g至2.0g):(5.0ml至9.0ml):(1.0ml至5.0ml)。The porous fiber composite membrane according to claim 6, wherein the functional resin: the third solvent: the fourth solvent is (0.5g to 2.0g): (5.0ml to 9.0ml): ( 1.0ml to 5.0ml).
  10. 如权利要求3所述之多孔纤维复合隔膜，其特征在于，所述制备方法进一步包括：The porous fiber composite membrane according to claim 3, wherein the preparation method further comprises:
    热处理步骤：自所述基材上收集所述多孔纤维复合隔膜并放置于一基板上，于一温度下热处理述多孔纤维复合隔膜。Heat treatment step: collecting the porous fiber composite diaphragm from the substrate and placing it on a substrate, and heat treating the porous fiber composite diaphragm at a temperature.
  11. 如权利要求12所述之制备方法，其特征在于，所述基板包括玻璃板。The manufacturing method according to claim 12, wherein the substrate comprises a glass plate.
  12. 如权利要求12所述之制备方法，其特征在于，所述温度介于100℃至150℃。The preparation method according to claim 12, wherein the temperature is between 100°C and 150°C.
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