CN108963158B - A kind of preparation method of polymer coating film containing P-O bond compound - Google Patents
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- 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
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Abstract
本发明涉及一种含P‑O键化合物的聚合物涂覆膜的制备方法，其特征是制备步骤如下：在反应釜中按照体积比（0.1～10）：1将丙酮、二甲基甲酰胺混合得到混合溶液，再加入混合溶液重量的0.5～2.5%重量的涂覆剂、聚偏氟乙烯‑六氟丙烯1～5%重量的和0.5～2.5%重量的聚甲基丙烯酸甲酯，超声波振荡10～50min；在50～90℃下搅拌8～12 h制得粘稠液体。在低温等离子体处理过的基膜上涂覆粘稠液体，通过干燥制得聚合物涂覆膜。本发明的原料成本较低，制备工艺简单，操作简便，耗时少，制备的涂覆膜用于电池体系中，可改善电池的放电性能，增大了电池的放电容量，改善电池的循环性能，为产业化打下良好的基础。
The invention relates to a preparation method of a polymer coating film containing a P-O bond compound, which is characterized in that the preparation steps are as follows: in a reaction kettle, acetone and dimethylformamide are mixed according to the volume ratio (0.1-10): 1 Mixing to obtain a mixed solution, then adding 0.5-2.5% by weight of the coating agent, 1-5% by weight of polyvinylidene fluoride-hexafluoropropylene and 0.5-2.5% by weight of polymethyl methacrylate based on the weight of the mixed solution, ultrasonic wave Shake for 10-50 min; stir at 50-90 °C for 8-12 h to obtain a viscous liquid. A viscous liquid is coated on the base film treated with low temperature plasma, and a polymer coating film is prepared by drying. The invention has the advantages of low cost of raw materials, simple preparation process, simple operation and less time-consuming, and the prepared coating film can be used in the battery system, which can improve the discharge performance of the battery, increase the discharge capacity of the battery, and improve the cycle performance of the battery , laying a good foundation for industrialization.
Description
Technical Field
The invention relates to a preparation method of a polymer coating film containing a P-O bond compound, in particular to a preparation method of a coating 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. In a battery system, the separator plays a role in preventing electron communication and conducting ions between the positive electrode and the negative electrode. The separator plays an important role in battery performance and safe use. Battery separators can be classified into dry-process membranes, wet-process membranes, and composite membranes, depending on the production process of the separator.
The preparation process of the dry film is to prepare the diaphragm by the steps of feeding, melt extrusion, stretching, cooling, heat treatment, stretching hole forming, heat setting, traction, slitting, rolling and the like of the polyolefin resin (Huang Yong bridge, and the like, ship electrical technology, 2011, 31(1): 26-29.). Depending on the stretching direction, dry processes can be divided into uniaxial stretching and biaxial stretching. The dry preparation method has the advantages of simple process, small pollution in the production process and high production efficiency and yield. The disadvantages of this method are the difficulty in controlling the pore size of the separator, the lateral tendency to crack, and the low safety and reliability.
The wet film is prepared through mixing liquid or small molecular matter with polyolefin resin, heating to melt into homogeneous mixture, cooling to separate phase and forming film. Heating the membrane to near melting point, and performing biaxial tension, heat preservation, solvent elution, etc. to obtain microporous membrane (Xudan, etc., plastics industry, 2013, 41(3): 94-97.). The separator prepared by this method has circular micropores. The micropores have the characteristics of small aperture, uniform pore distribution and the like.
The dry film process mainly uses PP raw material, and the wet film process mainly uses PE raw material. The composite film integrates the characteristics of a dry film and a wet film, and has the advantages of low pore closing temperature, high fusing temperature, low transverse shrinkage rate and the like.
Under abuse conditions, the lithium ion battery may be in a high temperature range of 100-300 ℃, and the lithium ion battery using the polyolefin film has potential safety hazards due to the fact that Polyethylene (PE), polypropylene (PP) and polyolefin composite films (such as PP/PE/PP and PE/PP) can shrink and deform at high temperature. In general, a polyolefin film is coated with a nanomaterial such as alumina to form a coated separator. In such a coated separator, the organic material imparts flexibility to the separator, meeting the requirements of battery assembly. At high temperature, the organic components can be melted to block the holes of the diaphragm, slow down or prevent the battery reaction and ensure the safety of the battery. The inorganic material is distributed on the outer layer of the diaphragm, plays the role of a rigid framework and ensures the safety of the lithium ion battery. The coated separator generally consists of a base film, a binder, and an inorganic nanomaterial.
Current coated separators generally use PVDF resins from a binder point of view [ Hennige v., et al, US 7790321, 2010.7.9.]And polymethyl methacrylate (PMMA) [ zhao jin bao, et al, chinese patent invention, CN 103035866 a, 2013.4.10.]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.]And polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) [ Jeong H.S., et al. electrochim. Acta, 2012, 86: 317-.]And (3) a binder. Sohn et Al combined polymethyl methacrylate (PMMA), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) and nano Al2O3As coating agent [ Sohn J. Y., et al., J. Solid State electrochem., 2012, 16, 551-Asn 556 ].]And coated on a PE film, a PVDF-HFP/PMMA coated separator was prepared.
Previous researches prove that the PVDF has larger regularity of molecular structure, the arrangement of polymer chains is compact, fluorine atoms and hydrogen atoms in the molecular chains have stronger hydrogen bond effect, and the tensile strength, the compressive strength, the impact toughness and the like of the polymer are larger. 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. Continuous contact of the adhesive with the adherend is called wetting, and obtaining a good wetting effect requires that the surface tension of the adhesive be smaller than the surface tension of the adherend. In the case of untreated polymers, such as polyethylene and polypropylene, the surface is more inert and difficult to bond.
Jeong et al Jeong h.s., et al, electrochim. Acta, 2012, 86: 317-. The content of the binder in the coating layer is increased, so that the falling of coating layer particles can be reduced, and the mechanical property of the diaphragm is improved. However, the binder-coated coating layer particles change the surface properties of the base film, reduce wettability to an electrolyte, and are disadvantageous to the performance of a battery used for large-current charge and discharge. 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 membrane and increasing the resistance of lithium ion diffusion across the membrane.
From the viewpoint of coating, 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 40nm2And coating a PE microporous membrane to prepare a coated diaphragm. Inorganic material with special pore channels is also used to replace nano Al2O3As a coating agent, in such separator-coated battery systems, solvated lithium ions are transported directly along the "green channel" provided by the inorganic particles.
From the view point of the base film, since the reactivity of the surface of the polyolefin base film is not large, the coating layer coated on the separator is not closely adhered to the base film. In the long-term charge and discharge process, the coating layer of the coating diaphragm is easy to fall off. In particular, untreated polyolefin compounds such as polyethylene and polypropylene are difficult to bond.
During long-term charge-discharge cycle, the powder falling phenomenon is easy to occur when the diaphragm is coated. To ameliorate this phenomenon, Chen et al [ Chen H., et al2 on polypropylene membranes for improved performances of lithium-ion batteries， J. Membr. Sci.，2014，458，217-224.]The surface of the PP film is treated by plasma technology and then coated with TiO2And a coated separator was prepared. Research shows that the plasma treatment can generate polar groups on the surface of the PP film, which is beneficial to TiO2Dispersion on the surface of the separator. The prepared diaphragm has higher liquid absorption rate, higher ionic conductivity and lower thermal shrinkage. The assembled lithium ion battery has higher specific discharge capacity and better rate discharge performance.
Despite the above modification studies, the application of the coated separator to a battery system has been problematic. For example, coating the separator increases the internal resistance of the battery, making it difficult to develop the battery discharge capacity. The dusting affects the safety performance of the battery. The coating has the problem of matching with a positive electrode, a negative electrode and electrolyte.
In order to solve the problems in the application of the coated diaphragm, 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 treated by the plasma to form the coating layer connected with the base film through the valuable bond, so that the bonding force between the coating layer coated in the coated diaphragm and the base film is obviously improved, the internal resistance of the battery is reduced, the discharge capacity of the battery is fully exerted, and the powder falling phenomenon is reduced. The compound containing P-O bond has strong wettability, strong affinity to electrolyte and strong liquid absorption capacity. The compatibility with the anode, the cathode and the electrolyte is good, and the performance of the coating film is 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 (0.1-10): 1 mixing acetone and dimethylformamide to prepare a mixed solution. Adding a coating agent accounting for 0.5-2.5% of the weight of the mixed solution, and carrying out ultrasonic oscillation for 1-30 min to obtain a uniformly mixed suspension. And adding polyvinylidene fluoride-hexafluoropropylene accounting for 1.0-5.0 wt% of the weight of the mixed solution into the suspension. And adding polymethyl methacrylate accounting for 0.5-2.5 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. Spreading a base film, treating one surface of the base film for 1 s-5 min or treating two surfaces of the base film for 1 s-5 min by using low-temperature plasma, coating viscous liquid on the surface of the treated base film, and performing vacuum drying or forced air drying at any temperature within a temperature range of 50-110 ℃ to obtain the polymer coating film.
The vacuum drying is heating drying under the pressure of 0.1-0.00001 atm.
The coating agent is phosphate of univalent cation, phosphate of divalent cation or phosphate of trivalent cation with the particle diameter ranging from 1nm to 5 mu m.
The phosphate of the trivalent cation is aluminum phosphate, scandium phosphate, iron phosphate, gallium phosphate or yttrium phosphate.
The phosphate of the divalent cation is magnesium phosphate, zinc phosphate, calcium phosphate, copper phosphate, strontium phosphate or barium phosphate.
The phosphate of the univalent cation is silver phosphate, lithium phosphate or cuprous phosphate.
The polyvinylidene fluoride-hexafluoropropylene is polyvinylidene fluoride-hexafluoropropylene with the average molecular weight of 20-280 ten thousand.
The polymethyl methacrylate is polymethyl methacrylate with the average molecular weight of 60-160 ten thousand.
The base film is a single-layer film or a multi-layer film.
The base film is a single-layer film of polypropylene or polyethylene film, or a multi-layer film containing a polypropylene layer.
The base film is a polypropylene or polyethylene single-layer film or a multi-layer film containing a polyethylene layer.
The single-layer film or the multilayer film is a diaphragm prepared by a dry process or a wet process in the diaphragm field.
The multilayer film is a diaphragm composed of single-layer films with the number of layers within the range of 2-10.
The raw material cost of the invention is lower, the preparation process is simple, the operation is simple and convenient, the time consumption is less, the prepared coating film is used in a battery system, although the impedance of the diaphragm can be increased to a certain extent, because the coating layer of the coating film, the battery pole piece and the base film can generate cohesive force, the impedance of the battery system and the polarization phenomenon in the charging and discharging process can be obviously reduced, and the discharging performance of the battery can be improved. In the long-term charge-discharge cycle process, the matching performance of the coating diaphragm with the anode, the cathode, the electrolyte and the like is obviously improved, the discharge capacity of the battery is increased, the cycle performance of the battery is improved, and a good foundation is laid for industrialization.
Drawings
Fig. 1 is a discharge capacity versus cycle number for a button cell at 1C rate current, a sample prepared in example 1 of the present invention.
FIG. 2 is an infrared image of the interface of the base film and the coating layer of the coating film produced in example 1 of the present invention.
FIG. 3 is an infrared image of the interface of the base film and the coating layer of the coating film produced in example 2 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 4: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding aluminum phosphate with particle size of 5nm in an amount of 1.25 wt% of the mixed solution, and ultrasonically oscillating for 15min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 150 ten thousand in an amount of 2.5% by weight based on the weight of the mixed solution and polymethyl methacrylate having an average molecular weight of 80 ten thousand in an amount of 1.25% by weight based on the weight of the mixed solution were added to the suspension, and the mixture was ultrasonically vibrated for 25 min. The reaction kettle was stirred at 60 ℃ for 9 h to convert the solution to a viscous liquid. The polypropylene single-layer film (with the thickness of 20 mu m) prepared by the dry film process is tiled, two surfaces of the single-layer film are respectively treated by low-temperature plasmas for 60s, and viscous liquid is respectively coated on the two surfaces of the treated single-layer film. The total thickness of the coating layers on both surfaces was made 12 μm, and vacuum-dried at 60 ℃ and 0.01 atm to obtain a polymer coating film.
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 putting the metal lithium, the prepared coating film, the positive plate, the battery shell and the electrolyte into a glove box filled with argon to assemble the CR2025 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 2.5-4.6V. The charge-discharge cycle experiment was performed at a current of 1C rate.
Example 2
In a reaction kettle, according to the volume ratio of 0.1: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Aluminum phosphate having a particle diameter of 1nm in an amount of 0.5% by weight based on the weight of the mixed solution was added. And ultrasonically oscillating for 1min to prepare a suspension which is uniformly mixed. Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) having an average molecular weight of 20 ten thousand in an amount of 1 wt% based on the weight of the mixed solution was added to the suspension, and polymethyl methacrylate (PMMA) having an average molecular weight of 60 ten thousand in an amount of 0.5 wt% based on the weight of the mixed solution was added thereto, and the mixture was ultrasonically oscillated for 10 minutes. The reaction kettle was stirred at 50 ℃ for 8h to convert the solution to a viscous liquid. The polyethylene single-layer film prepared by the wet process is laid flat, one surface of the single-layer film is treated for 1s by low-temperature plasma, and viscous liquid is coated on the surface of the treated single-layer film. Vacuum drying at 50 deg.C and 0.1 atm to obtain polymer coating film.
Example 3
In a reaction kettle, according to the volume ratio of 10: 1 mixing acetone and dimethylformamide to prepare a mixed solution. Iron phosphate having a particle size of 5 μm in an amount of 2.5% by weight based on the weight of the mixed solution was added. And ultrasonically oscillating for 30min to prepare a suspension which is uniformly mixed. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 280 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 160 ten thousand in an amount of 2.5% by weight of the mixed solution was further added thereto, followed by ultrasonic oscillation for 50 min. The reaction kettle was stirred at 90 ℃ for 12 h to convert the solution to a viscous liquid. The PP/PE/PP multilayer film obtained by compounding the PP and the PE film prepared by the dry film process is tiled, the surfaces of two PP layers of the PP/PE/PP multilayer film are respectively treated for 5min by low-temperature plasmas, viscous liquid is coated on the surface of the treated multilayer film, and the surface is dried in vacuum at 110 ℃ and 0.00001 atmospheric pressure to prepare the polymer coating film.
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. Magnesium phosphate was added in an amount of 2% by weight based on the weight of the mixed solution and having a particle size of 5 nm. And ultrasonically oscillating for 20min to obtain a uniformly mixed suspension. 3.3% by weight of the mixed solution and 30 ten thousand of polyvinylidene fluoride-hexafluoropropylene having an average molecular weight were added to the suspension, 1% by weight of the mixed solution and 80 ten thousand of polymethyl methacrylate were added thereto, and the mixture was ultrasonically oscillated for 20 min. The reaction kettle was stirred at 60 ℃ for 10 h to convert the solution to a viscous liquid. And (2) paving a PP/PE multilayer film obtained by compounding the PP and PE films prepared by the wet process, treating two surfaces of the multilayer film for 100s by using low-temperature plasmas respectively, coating viscous liquid on the two surfaces of the treated multilayer film, and drying in vacuum at 90 ℃ and 0.1 atmospheric pressure to obtain the polymer coating film.
Example 5
In a reaction kettle, according to the volume ratio of 0.1: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Adding calcium phosphate with the particle size of 5 mu m which is 1% of the weight of the mixed solution, and performing ultrasonic oscillation for 30min to obtain a uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 180 ten thousand in an amount of 5 wt% based on the weight of the mixed solution was added to the suspension. Then, polymethyl methacrylate having a weight of 1.4% of the weight of the mixed solution and an average molecular weight of 100 ten thousand was added thereto, and the mixture was ultrasonically vibrated for 15 min. The reaction kettle was stirred at 80 ℃ for 9 h to convert the solution to a viscous liquid. Spreading a PP/PP multilayer film obtained by compounding the polypropylene film prepared by the dry process, treating two surfaces of the multilayer film for 3 min by using low-temperature plasma respectively, coating viscous liquid on the two surfaces of the treated multilayer film respectively, and performing forced air drying at 50 ℃ to obtain the polymer coating film.
Example 6
In a reaction kettle, according to the volume ratio of 10: 1 mixing acetone and dimethylformamide to obtain a mixed solution. Silver phosphate having a particle size of 50nm in an amount of 2% by weight based on the weight of the mixed solution was added. And ultrasonically oscillating for 1min to prepare a suspension which is uniformly mixed. Polyvinylidene fluoride-hexafluoropropylene having a weight of 1% 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 2.5% by weight and an average molecular weight of 60 ten thousand based on the weight of the mixed solution was added thereto, and the mixture was ultrasonically oscillated for 50 min. The reaction kettle was stirred at 50 ℃ for 8h to convert the solution to a viscous liquid. The polypropylene single-layer film prepared by the dry process is tiled, one surface of the single-layer film is treated for 30s by low-temperature plasma, viscous liquid is coated on the treated single-layer film, and the single-layer film is dried in vacuum at 60 ℃ and 0.0008 atmosphere to prepare the polymer coating film.
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 phosphate with particle size of 100nm, and ultrasonically oscillating for 30min to obtain uniformly mixed suspension. Polyvinylidene fluoride-hexafluoropropylene having an average molecular weight of 260 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 90 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. Compounding the PP and PE films prepared by the wet process into a PP/PE multilayer film, tiling the PP/PE multilayer film, treating the surface of the PP layer of the multilayer film for 5min by using low-temperature plasma, coating viscous liquid on the treated surface, and drying in vacuum at 100 ℃ and 0.005 atmospheric pressure to obtain the polymer coating film.
Claims (7)
1. A method for preparing a polymer coating film containing a P-O bond compound, characterized in that the technical scheme comprises the following steps: in a reaction kettle, according to the volume ratio (0.1-10): 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 0.5-2.5 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, and treating one surface or two surfaces of the base film for 1 s-5 min by using low-temperature plasma; coating the viscous liquid on the surface of the treated base film, and performing vacuum drying or forced air drying at any temperature within a temperature range of 50-110 ℃ to obtain a polymer coating film;
the coating agent is phosphate of trivalent cation, divalent cation or monovalent cation;
the coating agent is a compound containing a P-O bond, and forms a coating layer connected with the base film through a valence bond by reacting the compound containing the P-O bond with the polyolefin base film treated by the plasma;
the phosphate of the trivalent cation is aluminum phosphate, scandium phosphate, iron phosphate, gallium phosphate or yttrium phosphate;
the phosphate of the divalent cation is magnesium phosphate, zinc phosphate, calcium phosphate, copper phosphate or barium phosphate;
the phosphate of the univalent cation is silver phosphate, lithium phosphate or cuprous phosphate.
2. The method of claim 1, wherein the vacuum drying is heating drying under a pressure of 0.1 to 0.00001 atm.
3. The method of claim 1, wherein the coating agent is a phosphate having a particle size in the range of 1nm to 5 μm.
4. The method of claim 1, wherein the polyvinylidene fluoride-hexafluoropropylene has an average molecular weight of 20 to 280 ten thousand.
5. The method of claim 1, wherein the polymethyl methacrylate is a polymethyl methacrylate having an average molecular weight of 60 to 160 ten thousand.
6. The process for producing a polymer-coated film containing a P-O bond compound according to claim 1, wherein said base film is a polypropylene or polyethylene single layer film, a multilayer film containing a polypropylene layer or a multilayer film containing a polyethylene layer.
7. The method of claim 6, wherein the number of layers of the multilayer film is in the range of 2 to 10.
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