WO2013159752A1 - 具有复合结构的纳米纤维锂离子电池隔膜材料及其制备方法 - Google Patents

具有复合结构的纳米纤维锂离子电池隔膜材料及其制备方法 Download PDF

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WO2013159752A1
WO2013159752A1 PCT/CN2013/074936 CN2013074936W WO2013159752A1 WO 2013159752 A1 WO2013159752 A1 WO 2013159752A1 CN 2013074936 W CN2013074936 W CN 2013074936W WO 2013159752 A1 WO2013159752 A1 WO 2013159752A1
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battery separator
lithium ion
ion battery
composite structure
nanofiber
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PCT/CN2013/074936
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English (en)
French (fr)
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吴大勇
孙鹤
王为希
梁卫华
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中国科学院理化技术研究所
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Publication of WO2013159752A1 publication Critical patent/WO2013159752A1/zh

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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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M50/429—Natural polymers
    • 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
    • H01M50/443—Particulate 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
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/20—Fibres of continuous length in the form of a non-woven mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • 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

  • Nanofiber lithium ion battery separator material with composite structure and preparation method thereof Nanofiber lithium ion battery separator material with composite structure and preparation method thereof
  • the invention belongs to the field of preparing nanofiber lithium ion battery separator by electrospinning, in particular, the invention relates to a nanofiber lithium ion battery separator with three-layer composite structure prepared by a large flow electrospinning method, and relates to the battery separator Preparation method.
  • the separator materials used in lithium ion batteries are still mainly composed of polyethylene or polypropylene microporous membranes formed by one-way or two-way stretching.
  • the main features of this type of product are: High level production technology has been formed in the United States, Japan and other countries, with good mechanical strength and stable performance.
  • the use of a polyolefin microporous membrane as a separator material is suitable for applications of small lithium ion batteries (such as batteries for mobile digital devices), and is not suitable for lithium ion batteries for electric vehicles and lithium ion batteries for energy storage.
  • the polyolefin has poor wettability with the lithium ion battery electrolyte;
  • the micropores formed in the separator material during the film formation process porosity The lower and usually the through hole, the membrane material has poor retention ability of the electrolyte;
  • the diaphragm material is more severely subjected to heat shrinkage, which brings obvious safety hazard to the battery.
  • Nanofiber separators are an important development direction for new lithium-ion battery separators. In recent years, material researchers in many countries have attached great importance to them.
  • the nanofiber membrane has the characteristics of large specific surface area, high porosity, uniform absorption of electrolyte, and can significantly improve the electrical properties and safety of the battery.
  • the disadvantages are low preparation efficiency and weak mechanical strength.
  • the Czech “nano-spider” is the representative of the non-spray electrospinning technology, and the two-dimensional electrospinning technology of China's warp and weft has developed the electrospinning technology with nozzles, see Chinese patent ZL200910087706.5, to the application level of industrial production. .
  • the application of warp and weft two-way electrospinning technology and other emerging high-efficiency electrospinning technologies such as electrospinning of airflow traction have solved the problem of nanomaterial preparation efficiency, which makes the practical and industrialization of nanofiber membrane materials possible.
  • the problem of the mechanical strength of the nanofiber membrane can also be solved by the design of the material structure and the subsequent process.
  • the present invention provides a battery separator having a three-layer composite structure.
  • an intermediate layer comprising a microporous film having thermal stability and an organic-inorganic composite system having a network structure
  • the composite structure of the outer layer of the composite material can improve the mechanical properties and thermal stability of the nanofiber membrane material battery separator while maintaining the advantageous properties of the nanofiber membrane material itself, thereby solving the problems faced by the existing materials.
  • One of the objects of the present invention is to provide a method for constructing a high thermal stability nanofiber lithium ion battery separator; second, providing a nanofiber lithium ion battery separator having a three-layer composite structure; and third, providing a high-flow electrospinning application Technology and equipment methods of making this material.
  • the invention provides a nanofiber lithium ion battery separator having a three-layer composite structure comprising an intermediate layer and an outer layer on both sides of the intermediate layer, and the outer layer material is sprayed on the surface of the intermediate layer by electrospinning to form a three-layer composite structure.
  • the composite structure is then post-treated by hot pressing or the like to obtain a three-layer composite material which is tightly bonded.
  • a nanofiber lithium ion battery separator having a composite structure comprising a first electrospinning spray layer, a thermally stable microporous film, and a second electrospinning spray is provided.
  • Floor a first electrospinning spray layer, a thermally stable microporous film, and a second electrospinning spray.
  • a method of forming a nanofiber lithium ion battery separator having a composite structure comprising the steps of:
  • first and second electrospun spray coating layers are also referred to as a first outer layer and a second outer layer, respectively, and a thermally stable microporous film at an intermediate position is also referred to as an intermediate layer.
  • the intermediate layer may be an electrospun sprayed film layer formed by electrospinning or a commercially available nonwoven film layer.
  • a method of forming a nanofiber lithium ion battery separator having a composite structure comprising the steps of: sequentially electrospinning spraying a first material, an intermediate layer material, and a second material to obtain a A composite structure battery separator of an electrospinning spray coating, an intermediate layer and a second electrospun spray coating.
  • the obtained battery separator having a composite structure is subjected to hot pressing treatment to achieve one or more of the following effects, improve mechanical strength of the separator material, increase crystallinity of the polymer material, and improve between different layers. Peel strength.
  • the intermediate layer acts as a support to provide high mechanical strength for lithium-ion batteries.
  • the first outer layer material and the second outer layer material differ from the materials used in the intermediate layer as a functional layer to ensure that the battery separator has specific chemical and physical properties.
  • the nanofiber membrane of the composite structure according to the present invention can be efficiently produced in large quantities using a large flow electrospinning technique and apparatus. As a battery separator for high-performance lithium-ion batteries, this nanofiber membrane can be used in small and power lithium-ion batteries to reduce battery internal resistance, improve battery life and charge and discharge performance.
  • the microporous film intermediate layer having thermal stability may be selected from the group consisting of polypropylene (PP), polyimide (PI), and polyester. (PET), polysulfone (PES), polymethyl methacrylate (PMMA:), aramid, non-woven fabric formed from one or more of a variety of celluloses that are insoluble in lithium ion battery electrolytes or Nanofiber film.
  • the interlayer film can be prepared by electrospinning or purchased directly from a commercial product.
  • the thickness used as the interlayer film is preferably controlled between 6 and 25 ⁇ m, depending on the specific needs of the application.
  • a person skilled in the art can select a suitable intermediate layer material according to the electrolyte system used in the target battery of the battery separator application to prevent the electrolyte from dissolving or swelling the intermediate layer material. If the applied electrolyte has a certain degree of dissolution of the battery separator, then other materials need to be selected.
  • the first outer layer and the second outer layer may be respectively selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polysulfone (PES), polyacrylonitrile ( PAN), formed from one or more materials of polymers such as aramid and cellulose.
  • PVDF polyvinylidene fluoride
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • PES polysulfone
  • PAN polyacrylonitrile
  • the first outer layer and the second outer layer may be respectively selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polysulfone (PES), polyacrylonitrile (PAN).
  • PVDF polyvinylidene fluoride
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • PES polysulfone
  • PAN polyacrylonitrile
  • the first outer layer and the second outer layer may each be selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polysulfone (PES), polyacrylonitrile ( PAN), one or more materials of polymers such as aramid and cellulose and aluminum oxides such as alumina, complexes with aluminum such as aluminum acetylacetonate, ie Al( aC ac) 3 , and chromium oxides It is formed of a complex formed of chromium oxide, titanium oxide, zinc oxide, zirconium oxide, and nanoparticles formed by one or more of other non-metal oxides such as silica, barium sulfate, and magnesium hydroxide.
  • PVDF polyvinylidene fluoride
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • PES polysulf
  • An inorganic nanoparticle material which can form a complex with polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, soluble polyimide, aramid, etc., and a method of adding and forming a composite with a polymer material includes The precursor of hydrolyzable-condensed to form a ceramic material such as silica is hydrolyzed in situ in a polymer solution of vinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, soluble polyimide, aramid or the like to form a network structure system; Alternatively, a nanoparticle finished powder such as silica, alumina, chromia, zirconia hydroxide or barium sulfate can be directly added and dispersed in a polymer solution to obtain a composite of a polymer material and a nanoparticle.
  • a ceramic material such as silica is hydrolyzed in situ in
  • a line electrospinning apparatus such as that disclosed in Chinese Patent Application No. CN2009 1 0087706.5 can be employed.
  • the first outer layer material may be sprayed on the first stage of the film formation area
  • the intermediate layer material may be sprayed on the second stage of the film formation area
  • the second outer layer material may be sprayed on the third stage of the film formation area on the film formation area.
  • the conveyor belt is subjected to the second segment and the third segment to receive the nanofiber film layer sprayed by the linear array nozzle group directly above the conveyor belt, and the conveyor belt enters the heat after the third segment.
  • the pressure treatment process section is collected by the winding device after being separated from the conveyor belt after shaping.
  • a large-flow electrospinning production apparatus in which 3N nozzle groups (N 1 ) are installed.
  • the nozzles are arranged perpendicularly to the forward direction of the conveyor belt.
  • Each nozzle group can be installed with 6 to 30 single needle nozzles, and the flow rate of each single needle nozzle can be set between l-20 mL/min.
  • the nozzle group is connected to the high voltage output of the DC high voltage power source, and the voltage can be set between several kilovolts and several tens of kilovolts depending on the material.
  • the nozzle of the nozzle group has a tip that is vertically downward, and the distance from the metal belt can be set in the range of 5-25 cm.
  • Electrospinning devices that can be used include, for example, single-needle nozzle electrospinning devices, multi-needle nozzle electrospinning devices, coaxial electrospinning devices, warp and weft bi-spinning devices, nozzleless electrospinning devices, and air-jet electrospinning Wire device, etc.
  • the obtained composite material was subjected to a hot press setting treatment using a hot press roll having a release coating on its surface.
  • the hot press setting can increase the density and mechanical strength of the composite structural film, and can improve the peel strength between the three layers of materials.
  • the hot pressing temperature is generally between 100 and 220 ° C depending on the material used.
  • the preparation of the intermediate layer material or the preparation of the first outer layer and the second outer layer material comprises the steps of: first formulating a solution of the polymer or polymer composite used, the inorganic polymer to be completely dissolved and blended
  • the nanometer can be uniformly dispersed in the solution; the concentration of the solution is adjusted so that the viscosity of the prepared solution is controlled at 500 ⁇ 1000 cP; the prepared polymer solution is sent to the nozzle group through the feed line by the feed pump, and the solution is in the high voltage DC electric field.
  • the role of the splitting and spraying on the metal conveyor belt is carried and accumulated into a film.
  • surface treatments such as corona treatment are required when necessary.
  • the structure of the nanofiber lithium ion battery separator having the three-layer composite structure according to the present invention is a three-dimensional pore structure formed by interweaving a plurality of nanofibers, and the porosity is between 40 and 70%, and has good gas permeability,
  • the electrolyte of a lithium ion battery has a strong absorption and retention function.
  • the material composition of the composite nanofiber membrane formed by the polymer and the nano ceramic is: the polymer material accounts for 60 to 90% of the mass percentage, and the inorganic nanoparticle, such as the ceramic material pellet, accounts for 10 to 40% by mass.
  • the nanofiber as the outer layer material usually has a diameter of between 100 and 600 nm. As the material of the intermediate layer, the fiber diameter can be selected from 200 ⁇ to 10 ⁇ .
  • the nanofiber lithium ion battery separator material having a three-layer composite structure wherein the interlayer preferably has a thickness of 6-25 ⁇ m, and the first outer layer material and the second outer layer material have a preferred thickness of 3 to 15 ⁇ m, the battery separator material.
  • the overall thickness is 12 ⁇ 55 ⁇ .
  • the nanofiber lithium ion battery separator with three-layer composite structure according to the invention has strong liquid absorption property, good heat stability, uniform pores, good thickness uniformity, high mechanical strength and ideal Electrical properties, can be used in automotive power lithium-ion batteries, including high-energy and high-power batteries, industrial lithium-ion batteries, such as energy storage Batteries, small lithium-ion batteries, such as batteries for electric bicycles and batteries for power tools and lithium-ion batteries for mobile digital devices.
  • Figure 1 Schematic diagram of a large flow electrospinning device.
  • Fig. 2 is a SEM photograph of an intermediate layer according to Embodiment 1 of the present invention.
  • Fig. 3 is a SEM photograph of the outer layer according to Example 1 of the present invention.
  • Fig. 4 is a SEM photograph of an intermediate layer according to Embodiment 2 of the present invention.
  • Figure 5 is a SEM photograph of the outer layer according to Example 2 of the present invention.
  • Figure 6 is a SEM photograph of the outer layer according to Example 3 of the present invention.
  • Figure 1 shows a schematic view of a high flow electrospinning apparatus employed in the present invention.
  • the apparatus includes three sets of head groups 1, a second section 2 and a third section 3, respectively located in the film forming zone, a metal conveyor belt 5 and a hot press setting device 4 located at the distal end of the metal conveyor belt.
  • Each set of nozzle groups is arranged perpendicular to the direction of travel of the metal conveyor belt 5.
  • a DC high voltage is applied between the spray head and the metal conveyor belt.
  • the three sets of nozzles can be sprayed with the same solution or with different solutions.
  • the type of solution can be selected by those skilled in the art depending on the type of battery separator.
  • PVDF polyvinylidene fluoride
  • DMF N,N-dimethylformamide
  • acetone a constant temperature of 30 ° C for 24 hours to obtain a clear and transparent solution A, wherein PVDF
  • the mass concentration is 8%; 9 g of silica nanoparticles with a diameter of about 200 nm is added to 100 g of DMF, ultrasonically dispersed for 3 hours, mixed with solution A, and ground at room temperature for 24 hours in a planetary ball mill to obtain a composite spinning.
  • the mass of the ceramic material in the composite spinning solution is 10% of the total mass of the polyvinylidene fluoride and the ceramic material.
  • the PVDF-nanosilica spinning solution prepared in the step (1) was conveyed by a gear pump to a large-flow electrospinning apparatus as illustrated in Fig. 1, and the infusion amount was, for example, 8 mL/needle/hour.
  • a DC high voltage is applied between the spray head and the conveyor belt, for example 25 kV.
  • the distance between the tip of the nozzle and the conveyor belt is, for example, 10 cm.
  • the head group performs a uniform reciprocating scanning motion perpendicular to the traveling direction of the conveyor belt at a speed of 100 mm/sec.
  • the metal conveyor travel speed is, for example, 2 m/min.
  • the three sets of nozzles of the first, second and third stages convey the same raw material solution, for example.
  • Electrospinning was carried out on the surface of the cellulose non-woven fabric under the conditions of an ambient temperature of 40 ° C and a humidity of ⁇ 20%. After spraying the first outer layer, the second outer layer was sprayed and sprayed, and the film was formed at 150 ° C. The temperature is subjected to roll forming treatment.
  • the surface SEM morphology of the interlayer film is as shown in FIG. 2, and the outer diameter of the PVDF-SiO2 in the composite nanofiber film obtained is about 200 nm, and the surface scanning electron microscope (SEM) morphology is as follows.
  • Figure 3 shows. After testing by hot box, the composite material has a shrinkage ratio of transverse and longitudinal directions of less than 1% after being kept at 180 ° C for 1 hour, and the material has good heat resistance.
  • a three-layer nanofiber composite lithium ion battery separator material with PI nonwoven fabric as intermediate layer/PVDF-HFP as outer layer PVDF-HFP/PI/PVDF-HFP
  • PVDF-HFP vinylidene fluoride-hexafluoropropylene copolymer
  • the PVDF-HFP spinning solution B prepared in the step (1) was conveyed by a gear pump to a large-flow electrospinning apparatus as shown in Fig. 1, and the infusion amount was, for example, 9 mL/needle/hour.
  • a DC high voltage for example 24 kV, is applied between the spray head and the conveyor belt.
  • the distance between the tip of the nozzle and the conveyor belt is set, for example, to 10 cm.
  • the head group performs a uniform reciprocating scanning motion perpendicular to the traveling direction of the conveyor belt at a speed of 100 mm/sec.
  • the metal conveyor travel speed is, for example, 2 m/min.
  • the three sets of nozzles located in the first, second and third sections of the film formation zone respectively transport the same raw material solution.
  • Electrospinning was carried out on the surface of the cellulose non-woven fabric under the conditions of setting the ambient temperature of 30 ° C and humidity to 50%, spraying the first outer layer and then spraying the second outer layer to form a film at 143 ° C.
  • the temperature is subjected to roll forming treatment. Comparing the surface micro-morphology of the film before and after hot pressing, the fiber diameter of the film formed after hot pressing is slightly increased ( ⁇ 10%), the crystallinity of the PVDF-HFP layer is increased, and the mechanical strength is increased from 26.4 MPa to 33.8 MPa.
  • the surface SEM topography of the interlayer film is as shown in FIG.
  • the diameter of the outer PVDF-HFP fiber in the PVDF-HFP/PI/PVDF-HFP composite film obtained by hot pressing is ⁇ 400 nm, and the surface scanning electron microscope (SEM) morphology is shown in Fig. 5.
  • SEM surface scanning electron microscope
  • the PVDF-HFP/PI/PVDF-HFP composites had a shrinkage ratio of less than 0.5% in both transverse and longitudinal directions after being heated at 220 °C for 1 hour.
  • the ionic conductivity of the separator was ⁇ 5 X 10 - 3 S/cm as measured by a button cell.
  • the raw material solution D prepared in the step (1) was conveyed by a gear pump to a large-flow electrospinning apparatus as shown in Fig. 1.
  • the infusion amount is, for example, 6 mL/needle/hour.
  • the head group performs a uniform reciprocating scanning motion, for example, at a speed of 60 mm/sec perpendicular to the traveling direction of the belt.
  • the metal conveyor has a travel speed of lm/min.
  • the three sets of nozzles in the first, second and third sections of the film forming zone respectively transport the same raw material solution; electrospinning is carried out on the surface of the cellulose non-woven fabric under the conditions of setting the ambient temperature of 45 ° C and the humidity to 40%. Spraying the first outer layer and then spraying the second outer layer to form a film, and then performing roll pressing treatment at a temperature of 160 ° C.
  • the prepared composite nanofiber membrane, the outer PVDF-in situ hydrolyzed SiO 2 fiber has a diameter of between 100 and 200 nm, and the surface scanning electron microscope (SEM) morphology is shown in Fig. 6. After tensile testing, the longitudinal and transverse tensile strengths of the material were approximately ⁇ 59 MPa.
  • the membrane has an ionic conductivity of ⁇ 3 X 10 - 3 S/cm as measured by a button cell.

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Abstract

本发明涉及一种具有复合结构的纳米纤维锂离子电池隔膜及其制备技术。该电池膜包括具有热稳定性的微孔薄膜中间层和位于中间层两侧的第一外层和第二外层，第一外层和第二外层为静电纺丝喷涂层。所述中间层与所述第一外层和第二外层可进一步通过热压结合。该电池隔膜的孔隙率在40%~70%之间。根据本发明的电池隔膜可应用大流量静电纺丝技术和设备高效地大量制备，并作为高性能锂离子电池隔膜应用于小型及动力锂离子电池中，起到提高电池安全性、降低电池内阻、延长电池循环寿命及提高电池充放电性能等作用。

Description

具有复合结构的纳米纤维锂离子电池隔膜材料及其制备方法 技术领域
本发明属于静电纺丝法制备纳米纤维锂离子电池隔膜领域， 特别地， 本发明涉及以大 流量静电纺丝法制备的具有三层复合结构的纳米纤维锂离子电池隔膜， 并涉及这种电池隔 膜的制备方法。
背景技术
目前， 锂离子电池使用的隔膜材料依然以单向或双向拉伸形成的聚乙烯、 聚丙烯微孔 膜为主。 这类产品的主要特点是： 在美、 日等国家已经形成了高水平的生产技术， 机械强 度较好， 性能比较稳定。 但是， 作为隔膜材料聚烯烃微孔膜比较适宜小型锂离子电池 （如 移动数码设备用电池） 的应用， 并不适宜电动车用锂离子电池以及储能用锂离子电池的应 用。 限制现有隔膜材料使用的原因有三个方面： 第一， 聚烯烃与锂离子电池电解液的亲润 性差； 第二， 在成膜过程中经拉伸形成在隔膜材料中的微孔， 孔隙率较低且通常为直通孔， 膜材料对电解液的保持能力差； 第三， 隔膜材料受热收縮现象较为严重， 对电池使用带来 明显的安全隐患。
纳米纤维隔膜是新型锂离子电池隔膜的一个重要发展方向， 近年来许多国家的材料研 究人员对其十分重视。 纳米纤维膜具有比表面积大、 孔隙率高、 均匀吸收电解液的特点并 可以明显提高电池的电性能和安全性， 其不足之处是制备效率偏低以及机械强度较弱。
捷克的 "纳米蜘蛛"是无喷头静电纺丝技术的代表， 而我国的经纬双向静电纺丝技术 则把有喷头的静电纺丝技术， 见中国专利 ZL200910087706.5 , 发展到了产业化生产的应用 水平。 应用经纬双向静电纺丝技术以及其它新兴的高效静电纺丝技术如气流牵引的静电纺 丝， 已经能很好地解决纳米材料制备效率的问题， 它使纳米纤维膜材料的实用和产业化成 为可能。 实际上， 纳米纤维膜机械强度的问题也可以通过材料结构的设计以及后续工艺处 理的方法得到解决。
车用动力锂离子电池以及储能锂离子电池对隔膜材料提出了很高的要求， 如较强的吸 液性能、 良好的受热稳定性、 均匀的孔隙、 很好的厚度均匀性等。 因此， 需要提供一种满 足上述要求的新型纳米纤维隔膜材料。
发明内容
针对锂离子电池对隔膜材料发展的要求， 本发明提供了一种具有三层复合结构的电池 隔膜。通过采用包括具有热稳定性的微孔薄膜中间层和具有网状结构的有机-无机复合体系 的复合材料的外层的复合结构， 可以提高纳米纤维膜材料电池隔膜的力学性能和热稳定 性， 同时保持纳米纤维膜材料本身的优势特性， 以此来解决现有材料面临的问题。
本发明的目的之一是提供一种构造高热稳定性纳米纤维锂离子电池隔膜的方法； 第 二， 提供具有三层复合结构的纳米纤维锂离子电池隔膜； 第三， 提供应用大流量静电纺丝 技术与设备制造该材料的方法。
本发明提供具有三层复合结构的纳米纤维锂离子电池隔膜包括中间层及位于中间层 两侧的外层， 外层材料以静电纺丝的方法喷涂在中间层的表面， 形成三层复合结构， 该复 合结构随后以热压等方法进行后处理， 得到结合紧密的三层复合材料。
根据本发明的一个方面， 提供一种具有复合结构的纳米纤维锂离子电池隔膜， 该电池 隔膜依次包括第一静电纺丝喷涂层，具有热稳定性的微孔薄膜， 以及第二静电纺丝喷涂层。
根据本发明的又一方面， 提供一种形成具有复合结构的纳米纤维锂离子电池隔膜的方 法， 该方法包括以下步骤：
通过静电纺丝在具有热稳定性的微孔薄膜的一侧形成第一静电纺丝喷涂层； 通过静电纺丝在所述具有热稳定性的微孔薄膜的另一侧形成第二静电纺丝喷涂层， 以 得到所述电池隔膜。
在本文中，为方便起见，第一和第二静电纺丝喷涂层也分别称为第一外层和第二外层， 位于中间位置的具有热稳定性的微孔薄膜也称为中间层。
优选地， 中间层可以是通过静电纺丝形成的静电纺丝喷涂薄膜层也可以是商业购买的 无纺布薄膜层。 根据本发明的再一方面， 提供一种形成具有复合结构的纳米纤维锂离子电 池隔膜的方法， 包括以下步骤： 依次静电纺丝喷涂第一材料， 中间层材料和第二材料， 以得到包括第一静电纺丝喷涂 层， 中间层以及第二静电纺丝喷涂层的复合结构电池隔膜。
优选地， 对得到的具有复合结构的电池隔膜进行热压处理， 以达到以下效果中的一种 或几种， 提高隔膜材料的机械强度、 提高高分子材料的结晶度以及提高不同层之间的剥离 强度。
中间层作为支撑体， 可为锂离子电池提供较高的机械强度。 第一外层材料和第二外层 材料与中间层所采用的材料不同， 作为功能层保证电池隔膜具有特定的化学和物理特性。 应用大流量静电纺丝技术和设备可以高效地大量制备根据本发明的复合结构的纳米纤维 膜。这种纳米纤维膜作为高性能锂离子电池的电池隔膜，可应用于小型及动力锂离子电池， 起到降低电池内阻、 提高电池寿命及充放电性能等作用。 优选地， 作为本发明所述三层复合材料的基础支撑体系——具有热稳定性的微孔薄膜 中间层， 可以是由选自聚丙烯 (PP)、 聚酰亚胺 (PI)、 聚酯 (PET)、 聚砜 (PES)、 聚甲基丙烯酸 甲酯 (PMMA：)、 芳纶、 不溶于锂离子电池电解液的多种纤维素中的一种或多种材料形成的 无纺布或纳米纤维薄膜。 中间层薄膜可以用静电纺丝的方式制备或直接购买商业化的产 品。 用作中间层薄膜的厚度优选控制在 6-25μηι之间， 根据应用的具体需要确定。 本领域 技术人员可以根据电池隔膜应用的目标电池所采用的电解液体系， 选择合适的中间层材 料， 以避免电解液对中间层材料产生溶解或溶胀。 如果所应用的电解液对电池隔膜有一定 程度的溶解， 则需要选择其它材料。
优选地， 第一外层和第二外层可以分别由选自包括聚偏氟乙烯 (PVDF), 聚偏氟乙烯- 六氟丙烯 (PVDF-HFP), 聚砜 (PES), 聚丙烯腈 (PAN), 芳纶和纤维素等聚合物中的一种或多 种材料形成。
优选地， 第一外层和第二外层可以分别由选自聚偏氟乙烯 (PVDF), 聚偏氟乙烯 -六氟 丙烯 (PVDF-HFP), 聚砜 (PES), 聚丙烯腈 (PAN), 芳纶和纤维素等聚合物中的一种或多种材 料与无机纳米颗粒形成的复合材料形成。
更优选地， 第一外层和第二外层可以分别由选自聚偏氟乙烯 (PVDF), 聚偏氟乙烯-六 氟丙烯 (PVDF-HFP), 聚砜 (PES), 聚丙烯腈 (PAN), 芳纶和纤维素等聚合物中的一种或多种 材料与铝的氧化物如氧化铝、 与铝的配合物如乙酰丙酮铝即 Al(aCac)3、 与铬的氧化物如氧 化铬、 二氧化钛、 氧化锌、 氧化锆及与其它非金属氧化物如二氧化硅、 硫酸钡、 氢氧化镁 中一种或多种的纳米颗粒形成的复合物等形成。
可与聚偏氟乙烯、聚偏氟乙烯 -六氟丙烯、 可溶性聚酰亚胺、 芳纶等形成复合物的无机 纳米颗粒材料， 其加入并与聚合物材料形成复合物的方法例如包括， 通过将可水解-縮合形 成二氧化硅等陶瓷材料的前躯体在偏氟乙烯、聚偏氟乙烯 -六氟丙烯、 可溶性聚酰亚胺、 芳 纶等聚合物溶液中原位水解形成网状结构体系； 或者可以将二氧化硅、 氧化铝、 氧化铬、 氧化锆氢氧化镁、 硫酸钡等纳米颗粒成品粉体直接加入并分散在聚合物溶液中可得到聚合 物材料与纳米颗粒的复合物。
为实现根据本发明的形成具有复合结构的电池隔膜的方法， 可以采用例如在中国专利 申请 CN2009 1 0087706.5中公开的生产线式静电纺丝设备。 例如， 可以在成膜区域的第一 段喷涂第一外层材料， 在成膜区域的第二段喷涂中间层材料， 在成膜区域的第三段喷涂第 二外层材料， 成膜区域上的传送带由第一段依次经第二段、 第三段接收位于传送带正上方 的线型阵列式喷头组以静电纺丝方式喷涂的纳米纤维薄膜层， 传送带经历第三段后进入热 压处理工艺段， 定型后经与传送带分离后由收卷装置收集。
优选地， 为实现 3层复合纳米纤维膜的制备， 优选采用安装 3N个喷头组（N 1 )的大 流量静电纺丝生产装置。 喷头组中喷头与传送带前进方向垂直布置， 每个喷头组可安装 6〜30个单针喷头， 每个单针喷头的流量可在 l-20mL/min之间设置。 喷头组与直流高压电 源输出的高压相连， 电压根据材料的不同可在几千伏〜几十千伏之间设置。 喷头组的喷头 尖端垂直向下， 与金属材质的传送带之间的距离可设置在 5-25cm范围内。 可采用的静电 纺丝装置例如包括单针喷头静电纺丝装置、 多针喷头静电纺丝装置、 同轴静电纺丝装置、 经纬双向静电纺丝装置、 无喷头静电纺丝装置及气流牵引静电纺丝装置等。
随后， 利用表面有防粘镀层的热压辊对得到的复合材料进行热压定型处理。 热压定型 的可提高复合结构薄膜的密度及机械强度， 并可提高三层材料之间的剥离强度。 通常， 根 据采用材料的不同， 热压温度一般在 100〜220°C之间。
优选地， 中间层材料的制备或者是第一外层和第二外层材料的制备包括以下步骤： 首 先配制所使用聚合物或聚合物复合物的溶液， 聚合物需完全溶解、 共混的无机纳米可以均 匀分散在溶液中； 调节溶液的浓度使所配制溶解的粘度控制在 500〜1000 cP; 用输料泵经 输料管线将配制好的聚合物溶液输送到喷头组， 溶液在高压直流电场的作用在裂分并喷涂 在金属传送带上被承载、 累积成膜。 但目前商业化的产品有时厚度过大或者均匀性不好， 在必要时需进行表面处理，例如电晕处理。在中间层表面喷涂外层材料后需经过厚度测定、 成型及干燥处理、 表面静电清除、 分切、 收卷等步骤来得到根据本发明的电池隔膜。
本发明所述的具有三层复合结构的纳米纤维锂离子电池隔膜的结构为由多层纳米纤 维交织而成的立体孔隙结构， 孔隙率在 40-70%之间， 具有良好的透气性能， 对锂离子电池 的电解液有很强的吸收和保持作用。 聚合物与纳米陶瓷等形成的复合纳米纤维膜的材料组 成为： 聚合物材料占质量百分比含量的 60〜90%， 无机纳米颗粒， 例如陶瓷材料颗粒， 所 占的质量百分比含量为 10〜40%； 作为外层材料的纳米纤维， 其直径通常在 100〜600 nm之 间。 作为中间层的材料， 所含的纤维直径可以在 200 ηηι〜10 μηι之间选择。
所述的具有三层复合结构的纳米纤维锂离子电池隔膜材料， 其中间层的优选厚度在 6-25μηι, 第一外层材料和第二外层材料的优选厚度在 3〜15μηι， 电池隔膜材料整体的厚度 在 12〜55μηι。
本发明所述的具有三层复合结构的纳米纤维锂离子电池隔膜， 具有较强的吸液性能、 良好的受热稳定性、 均匀的孔隙、 很好的厚度均匀性， 高的机械强度和理想的电性能， 可 用于车用动力锂离子电池， 例如包括高能量和高功率电池、 工业用锂离子电池， 例如储能 电池、 小型锂离子电池， 如电动自行车用电池和电动工具用电池和移动数码设备用锂离子 电池。
附图说明
图 1大流量静电纺丝设备示意图。
图 2为根据本发明实施例 1的中间层的 SEM照片。
图 3为根据本发明实施例 1的外层的 SEM照片。
图 4为根据本发明实施例 2的中间层的 SEM照片。
图 5根据本发明实施例 2的外层的 SEM照片。
图 6根据本发明实施例 3的外层的 SEM照片。
具体实施方式
下面结合具体实施例对本发明做进一步说明， 但本发明并不局限于以下实施例。 图 1示出本发明所采用的大流量静电纺丝设备的示意图。 该设备包括分别位于成膜区 域的第一段 1、 第二段 2和第三段 3的三组喷头组， 金属传送带 5和位于金属传送带远端 的热压定型装置 4。 每组喷头组垂直于金属传送带 5的行进方向布置。 在喷头和金属传送 带之间施加有直流高压。 三组喷头组可以喷涂相同的溶液， 也可以喷涂不同的溶液。 本领 域技术人员可以根据电池隔膜的种类选择溶液类型。
实施例 1
一种以纤维素无纺布为中间层 /聚合物 -陶瓷材料为外层的三层纳米纤维复合锂离子电 池隔膜材料
(1) 外层材料静电纺丝溶液的配制
将 80 g聚偏氟乙烯 (PVDF) 溶解于 650g N，N-二甲基甲酰胺 (DMF)和 276 g丙酮中， 恒 温 30°C下搅拌 24小时后得到澄清透明的 A溶液， 其中 PVDF的质量浓度为 8%; 将 9 g 直径约为 200 nm二氧化硅纳米粒子加入到 100g DMF中， 超声分散 3小时后与 A溶液混 合， 在室温下以行星式球磨机研磨 24 小时， 得到复合纺丝溶液。 复合纺丝溶液中陶瓷材 料的质量为聚偏氟乙烯和陶瓷材料总质量的 10%。
(2) 静电纺丝法制备聚合物 -陶瓷复合材料纳米纤维膜
将步骤 (1)制备的 PVDF-纳米二氧化硅纺丝溶液以齿轮泵输送到如附图 1示意的大流量 静电纺丝装置， 输液量例如为 8mL/针 /小时。 喷头和传送带之间施加有直流高压， 例如 25 kV。 喷头尖端与传送带间的距离例如为 10 cm。 喷头组以 lOOmm/sec的速度垂直于传送 带行进方向做匀速往复扫描运动。金属传送带行进速度例如为 2m/min。分别位于成膜区域 的第一、二、三段的三组喷头组输送例如同样的原料溶液。在设定环境温度 40°C、湿度〜 20% 条件下在纤维素无纺布表面进行电纺喷丝成， 喷涂第一外层后翻面喷涂第二外层， 成膜后 以 150°C的温度进行辊压定型处理。
该实施例中， 中间层薄膜的表面 SEM形貌如附图 2所示， 制得的复合纳米纤维膜中 外层 PVDF-SiO^†维的直径约为 200nm， 表面扫描电镜 (SEM)形貌如附图 3所示。 经热箱 测试， 该复合材料在 180°C恒温 1小时后横向与纵向的收縮比例均小于 1%， 该材料具有良 好的耐热性能。 该复合膜材料， 对碳酸乙烯酯:碳酸二甲酯:碳酸甲乙酯 (EC:DMC:EMC) = 1 :1 :1 的混合溶液的吸收量达到膜自身重量的〜 170%， 而单独检验中间层材料纤维素无纺 布， 其对 EC:DMC:EMC = 1 :1 :1的混合溶液的吸收能力仅为自重的〜 45%; 经制作扣式电池 检测， 该隔膜的离子电导率在 2〜3 X 10"3 S/cm之间。
实施例 2
一种以 PI无纺布为中间层 /PVDF-HFP为外层的三层纳米纤维复合锂离子电池隔膜材 料 (PVDF-HFP/PI/PVDF-HFP)
(1) 外层材料静电纺丝溶液的配制
将 80 g偏氟乙烯-六氟丙烯共聚物 (PVDF-HFP) 溶解于 450g DMF和 280 g丙酮中， 在 温度为 30°C下搅拌 24小时后得到澄清透明的 B溶液。
(2) PVDF-HFP/PI/PVDF-HFP三层复合纳米纤维锂离子电池隔膜的制备
将步骤 (1)制备的 PVDF-HFP纺丝溶液 B以齿轮泵输送到如附图 1示意大流量静电纺 丝装置， 输液量例如为 9 mL/针 /小时。 喷头和传送带之间施加直流高压例如 24 kV。 喷头 尖端与传送带间的距离例如设置为 10 cm。 喷头组以 lOOmm/sec的速度垂直于传送带行进 方向做匀速往复扫描运动。 金属传送带行进速度例如为 2m/min。 分别位于成膜区域第一、 二、 三段的三组喷头组输送同样的原料溶液。 在设定环境温度 30°C、 湿度〜 50%条件下在 纤维素无纺布表面进行电纺喷丝， 喷涂第一外层后翻面喷涂第二外层， 成膜后以 143°C的 温度进行辊压定型处理。 对比热压前后膜的表面显微形貌， 热压后构成薄膜的纤维直径略 有增大 (ΔΦ<10%)， PVDF-HFP层的结晶度提高， 机械强度由 26.4Mpa提高至 33.8Mpa。
该实施例中， 中间层薄膜的表面 SEM 形貌如附图 4 所示。 经热压制得的 PVDF-HFP/PI/PVDF-HFP 复合膜中外层 PVDF-HFP 纤维的直径〜 400 nm, 表面扫描电镜 (SEM)形貌如附图 5所示。 经热箱测试， 该 PVDF-HFP/PI/PVDF-HFP复合材料在 220 °C恒 温 1小时后横向与纵向的收縮比例均小于 0.5%。经制作扣式电池检测， 该隔膜的离子电导 率〜 5 X 10—3 S/cm。 实施例 3.
一种以 PP无纺布为中间层/ PVDF-原位水解 Si02为外层的三层纳米纤维复合锂离子电 池隔膜材料
(1) 外层材料静电纺丝溶液的配制
将 800 g聚偏氟乙烯 (PVDF) 溶解于 6000g DMF和 2800 g丙酮中， 恒温 30°C下搅拌 24小时后得到澄清透明的 C溶液； 将 90 mL水与 380 mL 四乙氧基硅烷 (TEOS)在搅拌下 依次加入溶液 C中， 在 30°C下机械搅拌 48小时得到原料溶液 D。
(2) 制备 PP无纺布为中间层 /PVDF-原位水解 Si02为外层的三层纳米纤维复合锂离子 电池隔膜
将步骤 (1)制备的原料溶液 D以齿轮泵输送到如附图 1示意大流量静电纺丝装置。输液 量例如为 6mL/针 /小时。 施加直流高压 20 kV， 喷头尖端与传送带间的距离设置为 15 cm。 喷头组例如以 60 mm/sec的速度垂直于传送带行进方向做匀速往复扫描运动。 金属传送带 行进速度为 lm/min。分别位于成膜区域第一、二、三段的三组喷头组输送同样的原料溶液; 在设定环境温度 45 °C、 湿度〜 40%条件下在纤维素无纺布表面进行电纺喷丝， 喷涂第一外 层后翻面喷涂第二外层， 成膜后以 160°C的温度进行辊压定型处理。
制得的复合纳米纤维膜， 外层 PVDF-原位水解 Si02纤维的直径在 100〜200nm之间， 表面扫描电镜 (SEM)形貌如附图 6所示。 经拉伸测试， 该材料的纵向与横向抗拉强度近似， 〜59MPa。 经制作扣式电池检测， 该隔膜的离子电导率在〜 3 X 10—3 S/cm。
以上借助优选实施例对本发明进行了详细说明， 但是本发明不限于此。 本技术领域技 术人员可以根据本发明的原理进行各种修改。 因此， 凡按照本发明原理所作的修改， 都应 当理解为落入本发明的保护范围。

Claims

权利要求书
1. 一种具有复合结构的纳米纤维锂离子电池隔膜， 该电池隔膜依次包括
第一静电纺丝喷涂层，
具有热稳定性的微孔薄膜， 以及
第二静电纺丝喷涂层。
2. 如权利要求 1 所述的具有复合结构的纳米纤维锂离子电池隔膜， 其特征在于， 所 述具有热稳定性的微孔薄膜为静电纺丝喷涂薄膜或无纺布薄膜。
3. 如权利要求 1 所述的具有复合结构的纳米纤维锂离子电池隔膜， 其特征在于所述 具有热稳定性的微孔薄膜为由选自包括聚丙烯 (PP)、 聚酰亚胺 (PI)、 聚酯 (PET)、 聚砜 (PES) , 聚甲基丙烯酸甲酯 (PMMA)、 芳纶、 不溶于锂离子电池电解液的纤维素组成的组的 一种或多种材料形成的无纺布或纳米纤维薄膜。
4. 如权利要求 1 所述的具有复合结构的纳米纤维锂离子电池隔膜， 其特征在于， 所 述第一静电纺丝喷涂层和第二静电纺丝喷涂层分别由选自聚偏氟乙烯 (PVDF)， 聚偏氟乙烯 -六氟丙烯 (PVDF-HFP) , 聚砜 (PES) , 聚丙烯腈 (PAN)、 芳纶和纤维素中的一种或多种材料 形成。
5. 如权利要求 1 所述的具有复合结构的纳米纤维锂离子电池隔膜， 其特征在于， 所 述第一静电纺丝喷涂层和第二静电纺丝喷涂层分别由选自聚偏氟乙烯 (PVDF)， 聚偏氟乙烯 -六氟丙烯 (PVDF-HFP) , 聚砜 (PES) , 聚丙烯腈 (PAN)、 芳纶和纤维素中的一种或多种与无 机纳米颗粒形成的复合材料形成。
6. 如权利要求 1 所述的具有复合结构的纳米纤维锂离子电池隔膜， 其特征在于， 所 述第一静电纺丝喷涂层和第二静电纺丝喷涂层分别由选自由聚偏氟乙烯 (PVDF)， 聚偏氟乙 烯-六氟丙烯 (PVDF-HFP) , 聚砜 (PES) , 聚丙烯腈 (PAN)、 芳纶和纤维素中一种或多种与二 氧化硅、 氧化铝、 二氧化钛、 氧化铬、 氧化锌、 氧化锆、 乙酰丙酮铝、 氢氧化镁、 硫酸钡 中的一种或多种的纳米颗粒或微米颗粒形成的复合材料形成。
7. 如权利要求 1 所述的具有复合结构的纳米纤维锂离子电池隔膜， 其特征在于， 所 述电池隔膜孔隙率为 40-70%。
8. 如权利要求 1 所述的具有复合结构的纳米纤维锂离子电池隔膜， 其特征在于所述 具有热稳定性的微孔薄膜的厚度为 6-25 μϋΐ, 所含纤维直径在 200ηηι-10μηι之间； 所述第 一静电纺丝喷涂层和第二静电纺丝喷涂层的厚度分别为 3-15μηι， 所含纤维直径在 100-600 nm之间， 且所述电池隔膜材料的厚度为 12-55μηι。
9. 如权利要求 1 所述的具有复合结构的纳米纤维电池隔膜的用途， 其特征在于， 用 于车用动力锂离子电池、 工业用锂离子电池、 小型锂离子电池和移动数码设备用锂离子电 池。
10. 一种形成具有复合结构的纳米纤维锂离子电池隔膜的方法， 包括以下步骤： 通过静电纺丝在具有热稳定性的微孔薄膜的一侧形成第一静电纺丝喷涂层； 通过静电纺丝在所述具有热稳定性的微孔薄膜的另一侧形成第二静电纺丝喷涂层， 以 得到所述复合结构隔膜。
11. 如权利要求 10所述的形成具有复合结构的纳米纤维锂离子电池隔膜的方法， 进 一步包括对得到的复合结构隔膜进行热压处理的步骤。
12. 如权利要求 10所述的形成具有复合结构的纳米纤维锂离子电池隔膜的方法， 其 中所述具有热稳定性的微孔薄膜是静电纺丝喷涂薄膜或无纺布薄膜。
13. 一种形成具有复合结构的纳米纤维锂离子电池隔膜的方法， 包括以下步骤； 依次静电纺丝喷涂第一材料， 中间层材料和第二材料， 以得到包括第一静电纺丝喷涂 层， 中间层以及第二静电纺丝喷涂层的复合结构隔膜。
14. 如权利要求 13 所述的形成具有复合结构的纳米纤维锂离子电池隔膜的方法， 进 一步包括对得到的复合结构隔膜进行热压处理的步骤。
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