CN108899460B - Preparation method of coating polymer film doped with aluminum phosphate coating agent - Google Patents
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention relates to a method for modifying a coating polymer film of different aluminum phosphates, which is characterized by comprising the following preparation steps: mixing acetone and dimethylformamide in a reaction kettle, adding a coating agent, and then adding polyvinylidene fluoride-hexafluoropropylene and polymethyl methacrylate to prepare viscous liquid. Coating the viscous liquid on the surface of the treated base film, and drying in vacuum or by blowing to obtain a coated polymer film. The coating agent is condensed aluminum phosphate, aluminum metaphosphate, aluminum phosphate gel or aluminum dihydrogen phosphate. The prepared coating polymer film has obviously improved matching with a positive electrode, a negative electrode, electrolyte and the like, and improves the cycle performance of the battery.
Description
Technical Field
The invention relates to a preparation method of a coating polymer film doped with an aluminum phosphate salt coating agent, in particular to a preparation method of a coating polymer film applicable to lithium batteries, lithium ion batteries, polymer batteries and super capacitors, and belongs to the technical field of battery diaphragm preparation.
Technical Field
The lithium ion battery has the advantages of high voltage, large capacity, no memory effect, long service life and the like, and is widely applied to digital products such as mobile phones, digital cameras, notebook computers and the like and power tools such as electric vehicles, hybrid electric vehicles and the like. Separators are important components of lithium ion batteries. Battery separators can be classified into dry-process membranes, wet-process membranes, and composite membranes, depending on the production process.
The dry film process mainly uses PP raw material, and the wet film process mainly uses PE raw material. The composite membrane combines the characteristics of a dry membrane and a wet membrane. The prepared composite film has the advantages of low closed pore temperature, high fusing temperature, low transverse shrinkage rate and the like.
In abuse situations, the lithium ion battery may heat up to 100 ℃, even 300 ℃. Since Polyethylene (PE), polypropylene (PP), and polyolefin composite films (e.g., PP/PE/PP, PE/PP) are subject to shrinkage deformation at high temperatures, lithium ion batteries using polyolefin films have potential safety hazards. The polyolefin film is coated with alumina and other nanometer material to form polymer coating film at home and abroad. The organic material in the coated polymer film makes the diaphragm flexible and meets the assembly requirement of the battery. At high temperature, organic components in the coating polymer film can be melted to block the holes of the diaphragm, so that the reaction of the battery is slowed down or prevented, and the aim of ensuring the safe use of the battery is fulfilled. The inorganic material in the coating polymer film is distributed on the outer layer of the diaphragm, plays the role of a rigid skeleton and improves the safety of the lithium ion battery. The coated polymer film generally consists of a base film, a binder and an inorganic nano material.
In terms of binders, PVDF resins are currently used for coating polymer films [ Hennige v., et al., US 7790321, 2010.7.9.]Polymethyl methacrylate (PMMA) [ quaternary, etc. ], functional material 2015, (46): 83-87.]Styrene Butadiene Rubber (SBR) [ Park J. H., et al., J. Power Sources, 2010, 195(24): 8306-.]Silica sol [ Lee j. r., et al., j. Power Sources, 2012, 216: 42-47.]Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) [ Jeong h. s., et al., electrochim. Acta, 2012, 86: 317-.]And the like. Korea et al [ Korea et al for lithium ion power electricityPVDF-HFP/PE coated Polymer film study of cells, Beijing: Press of university of Beijing Sizhi, 2015: 131-.]And the like, a PVDF-HFP/PE coated separator was prepared by a dip coating method using Polyethylene (PE) as a base material. Researches show that the PVDF-HFP coating can improve the wetting effect of the diaphragm on electrolyte, so that the assembled battery has excellent rate and cycle performance. Yi Yan hong et al [ Yi Yan hong et al, published molecular letters, 2012, 25(2): 172-.]PVDF and nano alumina are coated on a Polyethylene (PE) substrate, and a coated polymer film is prepared through phase inversion, so that the wetting capacity and stability of the separator are improved. Zhao Li et al (Zhao Li et al, inorganic materials academic newspaper, 2013, 28(2): 1296-1300).]Coating ZrO on the surface of Celgard membrane by using PVDF as binder2And (4) coating. Research shows that the coating can obviously improve the thermal stability of the size of the diaphragm and the wettability of the diaphragm to electrolyte. However, excessive binder in the coating layer tends to cause the accumulation of the nanomaterial in the pores of the separator, reducing the porosity of the coated separator. Previous studies have shown that the PVDF has a strong structural regularity, a tight arrangement of the polymer chains, and strong hydrogen bonds between fluorine atoms and hydrogen atoms in the molecular chains. The polymer has high tensile strength, compressive strength, impact toughness and the like.
Adsorption theory holds that adhesion is caused by intermolecular contact and interfacial forces of the two materials. The main sources of adhesion are intermolecular forces, including hydrogen bonding and van der waals forces. When the adhesive is continuously brought into contact with an adherend called wetting, obtaining a good bonding effect requires that the surface tension of the adhesive be smaller than the surface tension of the adherend. Untreated polymers (e.g., polyethylene, polypropylene) have surfaces that are more inert and difficult to bond.
Jeong et al [ Jeong H.S., et al, electro Acta, 2012, 86: 317-. The addition of the binder in the coating layer can reduce the falling of coating particles and improve the mechanical property of the diaphragm. However, the coated particles coated with the binder change the surface properties of the base film, reduce wettability to the electrolyte, and are disadvantageous for high-current charge and discharge performance for a battery system. Song et al [ Song J., et al. Electrochim. Acta, 2012, 85: 524-530 ] found that nano-coated particles are easily accumulated in the pores of the base film under the action of the binder, reducing the porosity of the coated polymer film and increasing the resistance of lithium ion diffusion across the membrane.
From the viewpoint of the applied coating, the inorganic materials that have been studied include nano Al2O3、ZrO2、SiO2、TiO2、MgO、CaO、CaCO3、BaSO4Zeolites, boehmites, clays, and the like. Takemura et al [ Takemura D., et al. J. Power Sources, 2005, 146(1/2): 779-.]Examine Al2O3The effect of particle size on the performance of the separator. They found that Al was coated2O3The high temperature resistance of the separator can be improved. Choi et al [ Choi E.S., et al J. Mater. chem., 2011, (38): 14747-14754.]With SiO having a particle size of 40nm2Coating a PE microporous membrane to prepare a coated polymer membrane. Inorganic materials of special pore channels are also used as coating agents for preparing coated separators. In such coated polymer films, solvated lithium ions can pass through the interstices of the inorganic particles and travel directly along the "green channel" provided by the inorganic particles.
From the base film, since the polyolefin film has low surface reactivity, the coating layer coated on the polymer film is not tightly adhered to the base film. In the process of long-term charge and discharge, the coating layer coated on the surface of the polymer film is easy to fall off. Untreated polyolefin separators (e.g., polyethylene, polypropylene) are difficult to bond and dusting is severe.
The coated polymer film is prone to dusting during long-term charge-discharge cycling. To improve this phenomenon, Chen et al [ Chen H., et al., J. Membr. Sci., 2014, 458, 217-.]The surface of the PP film is treated by plasma technology and then coated with TiO2To produce a coated polymer film. Research shows that plasma treatment can generate polar groups on the surface of the PP film, which is beneficial to TiO2Dispersion over the surface of the membrane. The prepared diaphragm has higher liquid absorption rate, higher ionic conductivity and lower thermal shrinkage rate. The assembled lithium ion battery has higher discharge capacity and better rateAnd (4) electrical property.
Despite the above modification efforts, the application of coated polymer membranes in battery systems remains problematic. For example, the applied coating layer increases the internal resistance of the battery, making it difficult to develop the discharge capacity of the battery. The dusting affects the safety performance of the battery. The coating layer has matching performance with the anode, the cathode and the electrolyte.
In order to solve the problems in the application of coating the polymer film, the compound containing the P-O bond is added into the coating layer, and the compound containing the P-O bond reacts with the polyolefin base film to form the coating layer connected with the base film through the valuable bond, so that the bonding force between the coating layer and the base film in the coating polymer film can be obviously improved, the internal resistance of the battery is reduced, and the discharge capacity of the battery is fully exerted. The compound containing the P-O bond has strong wettability and strong affinity to the electrolyte. The matching property with the anode, the cathode and the electrolyte is good, and the performance of the coating polymer film can be obviously improved.
Disclosure of Invention
The technical scheme adopted by the invention comprises the following steps:
in a reaction kettle, according to the volume ratio (0.1-12): 1 mixing acetone and dimethylformamide to prepare a mixed solution. Adding a coating agent accounting for 0.5-2.5 wt% of the mixed solution, and performing ultrasonic oscillation for 1-30 min to obtain a uniformly mixed suspension. And adding polyvinylidene fluoride-hexafluoropropylene accounting for 1-5 wt% of the mixed solution into the suspension. And adding polymethyl methacrylate accounting for 1-2.5 wt% of the mixed solution. And (4) carrying out ultrasonic oscillation for 10-50 min. Stirring for 8-12 h at 50-90 ℃ to convert the solution in the reaction kettle into viscous liquid. And (3) spreading the base film subjected to radiation treatment on an aluminum plate, coating the viscous liquid on the surface of the base film subjected to radiation treatment, and performing vacuum drying or forced air drying at any temperature within a temperature range of 50-120 ℃ to obtain the coating polymer film doped with the aluminum phosphate salt coating agent.
The base film after radiation treatment is to treat one surface or two surfaces of the base film for 10 s-15 min under glow discharge, corona discharge, radio frequency low-temperature plasma discharge or jet flow low-temperature plasma discharge.
The coating agent is condensed aluminum phosphate, aluminum metaphosphate, aluminum phosphate gel or aluminum dihydrogen phosphate with the particle size ranging from 1nm to 5 mu m.
The polyvinylidene fluoride-hexafluoropropylene is polyvinylidene fluoride-hexafluoropropylene with the average molecular weight of 50-300 ten thousand.
The polymethyl methacrylate is polymethyl methacrylate with the average molecular weight of 100-200 ten thousand.
The base film is a single-layer film or a multi-layer film containing a polypropylene or polyethylene layer.
The multilayer film is a diaphragm composed of single-layer films with the number of layers within the range of 2-10.
The preparation method has the advantages of low raw material cost, simple preparation process, simple and convenient operation and less time consumption, and the prepared coating polymer film applied to a battery system can obviously reduce the internal resistance of the battery, obviously improve the matching property with materials such as a positive electrode, a negative electrode, electrolyte and the like, increase the exertion of the discharge capacity of the battery, improve the cycle performance of the battery and lay a good foundation for industrialization.
Drawings
FIG. 1 is an IR spectrum of the interface of a base film and a coating layer of a coated polymer film of example 1 of the present invention.
FIG. 2 is an impedance plot of an acyclic sample and a sample charged and discharged with 40 cycles of a button cell prepared in example 1 of the present invention
Detailed Description
The present invention will be further described with reference to the following examples. The examples are merely further additions and illustrations of the present invention, and are not intended to limit the invention.
Example 1
In a reaction kettle, according to a volume ratio of 6: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding 1.25 wt% of condensed aluminum phosphate with particle size of 100 nm based on the weight of the mixed solution, and ultrasonically oscillating for 15min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having a weight of 2% by weight and an average molecular weight of 100 ten thousand based on the weight of the mixed solution was added to the suspension, and polymethyl methacrylate having a weight of 3.3% by weight and an average molecular weight of 120 ten thousand based on the weight of the mixed solution was added thereto, and the mixture was ultrasonically oscillated for 25 min. The solution in the reaction kettle was converted to a viscous liquid by stirring at 70 ℃ for 9 h. After a polypropylene single-layer film (with the thickness of 10 mu m) is tiled, one surface of the single-layer film is treated for 100s by glow discharge, viscous liquid is coated on the surface of the treated polypropylene single-layer film, single-side coating is carried out, the coating thickness is 12 mu m, and vacuum drying is carried out at 100 ℃ to obtain the coating polymer film doped with the condensed aluminum phosphate coating agent.
Will form Li1.05Ni0.5Co0.2Mn0.3O2The type ternary positive electrode material, the acetylene black and the PVDF binder are weighed according to the weight ratio of 85:10:5, N-methyl pyrrolidone is used as a grinding aid, and ball milling and mixing are carried out for 3 hours to prepare uniform slurry. And coating the uniform slurry on an aluminum foil current collector, and drying to obtain the positive plate. And placing the metal lithium, the prepared polymer coating film, the positive plate, the battery shell and the electrolyte into a glove box filled with argon atmosphere to assemble the CR2025 type button battery. And (3) carrying out charge-discharge and cycle performance test on the prepared button cell on a new Will cell test system. The test temperature was normal temperature (25. + -. 1 ℃). The charging and discharging interval is 2.5-4.3V. The charge-discharge cycle experiment was performed at a current of 1C rate. The charge and discharge experiments show that the discharge capacity of the prepared sample at the 1 st cycle is 175 mAh/g.
Example 2
In a reaction kettle, according to the volume ratio of 0.1: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding condensed aluminum phosphate with the particle size of 1nm accounting for 0.5 percent of the weight of the mixed solution, and performing ultrasonic oscillation for 1min to prepare a uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 200 ten thousand in an amount of 1% by weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 100 ten thousand in an amount of 1% by weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 10 min. The reaction kettle was stirred at 50 ℃ for 8h to convert the solution to a viscous liquid. After the polyethylene single-layer film is laid flat, two surfaces of the single-layer film are respectively treated for 10s under the radio frequency low-temperature plasma discharge condition. And (3) coating the viscous liquid on the surface of the treated polyethylene single-layer film, and drying in vacuum at 120 ℃ to prepare the coating polymer film doped with the condensed aluminum phosphate coating agent.
Example 3
In a reaction kettle, according to the volume ratio of 12: 1 mixing acetone and dimethylformamide to prepare a mixed solution. Adding aluminum metaphosphate with particle size of 5 μm and weight of 2.5% of the mixed solution, and ultrasonically oscillating for 30min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 50 ten thousand in an amount of 5% by weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 200 ten thousand in an amount of 2.5% by weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 50 min. The solution in the reaction kettle was converted to a viscous liquid by stirring at 90 ℃ for 12 h. After the PP/PE/PP multilayer film is laid flat, the PP/PE/PP multilayer film is placed under radio frequency low-temperature plasma discharge, and two surfaces of the multilayer film are respectively treated for 15 min. The viscous liquid was coated on both treated surfaces and dried under vacuum at 50 ℃ to produce a coated polymer film doped with aluminum metaphosphate coating agent.
Example 4
In a reaction kettle, mixing the raw materials in a volume ratio of 1: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding 2 wt% of the mixed solution and 150nm aluminum metaphosphate, and ultrasonically oscillating for 20min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 130 ten thousand in an amount of 5% by weight based on the weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 150 ten thousand in an amount of 1% by weight based on the weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 20 min. The solution in the reaction kettle was converted to a viscous liquid by stirring at 90 ℃ for 10 h. After the PP/PE multilayer film is laid flat, the PP/PE multilayer film is placed under the condition of jet low-temperature plasma discharge, and the PP surface of the multilayer film is treated for 10 min. And (3) coating the viscous liquid on the surface of the treated multilayer film, and drying by blowing at 90 ℃ to prepare the coating polymer film doped with the aluminum metaphosphate coating agent.
Example 5
In a reaction kettle, according to a volume ratio of 0.5: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding aluminum phosphate gel with particle diameter of 200nm and weight percent of 1% of the mixed solution, and ultrasonically oscillating for 20min to obtain uniformly mixed suspension. 3.3% by weight of the mixed solution and 50 ten thousand of polyvinylidene fluoride-hexafluoropropylene having an average molecular weight were added to the suspension, 1.4% by weight of the mixed solution and 100 ten thousand of polymethyl methacrylate were added thereto, and the mixture was ultrasonically oscillated for 50 min. The solution in the reaction kettle was converted to a viscous liquid by stirring at 90 ℃ for 9 h. After laying the PP/PP multilayer film flatly, the two surfaces of the multilayer film are respectively treated for 100s under the glow discharge condition. And (3) coating the viscous liquid on the surface of the treated multilayer film, and performing forced air drying at 50 ℃ to obtain the coated polymer film doped with the aluminum phosphate gel coating agent.
Example 6
In a reaction kettle, according to the volume ratio of 12: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding aluminum phosphate gel with particle diameter of 50nm in an amount of 2.5 wt% of the mixed solution, and ultrasonically oscillating for 1min to obtain uniformly mixed suspension. 3.3% by weight of the mixed solution and 300 million by weight of polyvinylidene fluoride-hexafluoropropylene were added to the suspension, and 2.5% by weight of the mixed solution and 200 million by weight of polymethyl methacrylate were added thereto, followed by ultrasonic oscillation for 30 min. The reaction kettle was stirred at 50 ℃ for 8h to convert the solution to a viscous liquid. After laying the single-layer film of the polypropylene film, one surface of the single-layer film is treated for 100s under the condition of glow discharge. And (3) coating the viscous liquid on the surface of the treated single-layer film, and drying the film in vacuum at 80 ℃ to prepare the coated polymer film doped with the aluminum phosphate gel coating agent.
Example 7
In a reaction kettle, according to a volume ratio of 5:1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding 0.67 wt% of the mixed solution and aluminum dihydrogen phosphate with particle diameter of 1nm, and ultrasonically oscillating for 30min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 100 ten thousand in an amount of 2% by weight of the mixed solution was added to the suspension, and polymethyl methacrylate having an average molecular weight of 120 ten thousand in an amount of 2% by weight of the mixed solution was added thereto, followed by ultrasonic oscillation for 20 min. The solution in the reaction kettle was converted to a viscous liquid by stirring at 70 ℃ for 12 h. And (2) tiling the PP/PE multilayer film, placing the PP/PE multilayer film under the condition of jet low-temperature plasma discharge, treating the PE surface of the multilayer film for 20s, coating viscous liquid on the surface of the treated multilayer film, and performing forced air drying at 100 ℃ to obtain the coating polymer film doped with the aluminum dihydrogen phosphate coating agent.
Claims (7)
1. A preparation method of a coating polymer film doped with aluminum phosphate salt coating agent is characterized by adopting the technical scheme comprising the following steps:
in a reaction kettle, according to the volume ratio (0.1-12): 1, mixing acetone and dimethylformamide to prepare a mixed solution; adding a coating agent accounting for 0.5-2.5 wt% of the mixed solution, and performing ultrasonic oscillation for 1-30 min to obtain a uniformly mixed suspension; adding polyvinylidene fluoride-hexafluoropropylene accounting for 1-5 wt% of the mixed solution into the suspension; adding polymethyl methacrylate accounting for 1-2.5 wt% of the mixed solution; carrying out ultrasonic oscillation for 10-50 min; stirring for 8-12 h at 50-90 ℃ to convert the solution in the reaction kettle into viscous liquid; spreading the base film subjected to radiation treatment on an aluminum plate, coating the viscous liquid on the surface of the base film subjected to radiation treatment, and performing vacuum drying or forced air drying at any temperature within a temperature range of 50-120 ℃ to prepare a coated polymer film;
the base film is a polyolefin base film;
the coating agent is a compound containing a P-O bond, and reacts with the polyolefin-based film by virtue of the compound containing the P-O bond.
2. The method as claimed in claim 1, wherein the coating agent is condensed aluminum phosphate, metaphosphate, aluminum phosphate gel or aluminum dihydrogen phosphate with a particle size ranging from 1nm to 5 μm.
3. The method of claim 1, wherein the polyvinylidene fluoride-hexafluoropropylene is polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 50-300 ten thousand.
4. The method of claim 1, wherein the polymethylmethacrylate is a polymethylmethacrylate having an average molecular weight of 100 to 200 ten thousand.
5. The method of claim 1, wherein the radiation-treated base film is a base film obtained by subjecting one or both surfaces to glow discharge, corona discharge, radio-frequency low-temperature plasma discharge or jet low-temperature plasma discharge for 10s to 15 min.
6. The method of claim 1 wherein the base film is a monolayer or multilayer film comprising a polypropylene or polyethylene layer.
7. The method of claim 6, wherein the multilayer film is a separator comprising a single layer of film having a number of layers in the range of 2 to 10.
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