CN103073772A - Preparation method of ultra high molecular weight polyethylene/biomass nanocrystalline composite membrane - Google Patents
Preparation method of ultra high molecular weight polyethylene/biomass nanocrystalline composite membrane Download PDFInfo
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- CN103073772A CN103073772A CN2013100210378A CN201310021037A CN103073772A CN 103073772 A CN103073772 A CN 103073772A CN 2013100210378 A CN2013100210378 A CN 2013100210378A CN 201310021037 A CN201310021037 A CN 201310021037A CN 103073772 A CN103073772 A CN 103073772A
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Abstract
The invention relates to a preparation method of an ultra high molecular weight polyethylene/biomass nanocrystalline composite membrane. The existing polyethylene and polypropylene membranes are difficult to meet the requirement on light weight of lithium batteries. The method comprises the steps of preparing fibrous biomass nanocrystalline, adding stearic acid into sulfoxide chloride to be conducted to stirring and backflow, pumping solvent under nitrogen protection, so as to obtain stearic acid with the end group being conducted to acylating chlorination, dispersing the fibrous biomass nanocrystalline in methylene dichloride through an ultrasonic dispersion method, adding the fibrous biomass nanocrystalline into the stearic acid with the end group being conducted to acylating chlorination to be conducted to stirring and backflow for 1 to 3 days, so as to obtain biomass nanocrystalline of surface grafted stearic acid, then mixing the biomass nanocrystalline of surface grafted stearic acid into solution of swelling ultra high molecular weight polyethylene resin, obtaining a jelly membrane after shaping through water bath, and finally performing two-way stretching, extracting, drying and thermoforming, so as to obtain a composite battery membrane. The battery membrane prepared through the method has the advantages that the thickness is 4 to 40 micrometers, the amount of porosity is 30 to 55 percent, both the longitudinal tensile strength and the horizontal tensile strength are larger than 200MPa, and melting breakage temperature is raised to 155 DEG C from 145 DEG C.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of preparation method of ultrahigh molecular weight polyethylene/biomass nanocomposite barrier film.
Technical background
Lithium ion battery because of have operating voltage height, energy density high, have extended cycle life, quality is light, volume is little and the characteristic of the excellence such as pollution-free becomes the focus of in recent years novel power supply technical study and developed rapidly, become main force's power supply of each electronic product, be widely used at present the electronic product fields such as mobile phone, portable computer, photographic camera, pick up camera, also can be used as the required electrical source of power of electromobile and hybrid vehicle etc.In the structure of lithium cell, barrier film is one of crucial interior layer assembly, the performance of barrier film has determined interface structure, internal resistance of battery etc., directly affect the characteristics such as capacity, cycle performance and safety performance of battery, the barrier film of excellent performance has very important effect to the over-all properties that improves battery.Because microporous polyolefin film has higher porosity, lower resistance, higher tearing toughness, preferably antiacid alkali ability, good elasticity and to the retention of aprotic solvent, so microporous polyolefin film becomes topmost lithium ion battery separator material.
The development trend of lithium cell is that volume is more and more less, quality is more and more lighter, so the thickness of the lithium battery diaphragm that needs is also more and more thinner, but require again barrier film to have the intensity that reaches safety requirements, this just has higher requirement to the mechanical property of barrier film, and common polyethylene and polypropylene diaphragm have been difficult to satisfy the light-weighted requirement of lithium cell.And ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is higher by the barrier film intensity of thermally induced phase separation preparation, and aperture and porosity can be regulated and control, and the easy serialization of preparation process becomes an important technology trends from now on.Along with lithium ion battery applications is more and more extensive, security also becomes more and more important, wherein how to prevent internal temperature of battery raise the fusing point reach lithium or electrolytic solution point of ignition and cause the subject matter that becomes the barrier film development of fire failure.The heat that forms owing to the lithium ion battery short circuit so that internal temperature of battery raise, the inaccessible blocking-up of micropore electric current passes through when the battery diaphragm temperature arrives closed pore temperature, but thermal inertia can make temperature further rise, might reach the melt fracture temperature and cause membrane ruptures, therefore, the closed pore temperature of battery diaphragm and melt fracture temperature differ and are the bigger the better.Difference between UHMWPE membrane ruptures temperature and the closed pore temperature only has 15 ℃ (130 ℃ of closed pore temperatures, 145 ℃ of barrier film melt fracture temperature), is the safer key of UHMWPE lithium ion battery separator so improve the melt fracture temperature of UHMWPE barrier film.
If in the UHMWPE barrier film, add a kind of electronic isolation, dystectic nanofiber, the network that in barrier film, forms by nanofiber and the formation of nanofiber induced surface extended-chain crystal, can not only improve the melt fracture temperature of UHMWPE barrier film, also can improve the mechanical property of UHMWPE barrier film.The biomass nano crystalline substance is a kind of novel poly-polysaccharide nano-crystalline, and following advantage is arranged in actual use: (1) biomass nano crystalline substance is a kind of organic nanofibers, electronic isolation, and fusing point is greater than 250 ℃; (2) starting material wide material sources, cheap, renewable; (3) have lower density, can excessively not increase material proportion after the filling; (4) have rigidity characteristic, demonstrate high strength and modulus, the modulus nanocrystalline such as Mierocrystalline cellulose can reach 145GPa; (5) rich surface hydroxyl, easier realization surface modification, the easier dispersion stabilization that is implemented in the varying environment.So, by in the UHMWPE barrier film, adding the biomass nano crystalline substance, can significantly improve the melt fracture temperature of UHMWPE barrier film, improve the security of lithium ion battery.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, a kind of preparation method of ultrahigh molecular weight polyethylene/biomass nanocomposite barrier film is provided.
The inventive method may further comprise the steps:
Step (1). it is brilliant to prepare fibrous biomass nano, and described fibrous biomass nano crystalline substance is that Mierocrystalline cellulose is nanocrystalline or chitin is nanocrystalline;
Preparing the nanocrystalline method of Mierocrystalline cellulose is: cellulose crystallite is added the sulphuric acid soln that mass content is 40～60 ﹪, wherein the mass ratio of cellulose crystallite and sulphuric acid soln is 4～10:100,20～60 ℃ of lower 1～6h that stir, add deionized water and dilute, obtaining the nanocrystalline concentration of Mierocrystalline cellulose is the suspension of 10～15g/L; Suspension is centrifugal, removes supernatant liquor, will precipitate the adding deionized water and dilute, and obtains the acidic suspension that cellulose crystallite concentration is 20～40g/L; The acidic suspension that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 2～6 hours, until the pH value to 5 of acidic suspension～7 in the dialysis tubing; Acidic suspension lyophilize after the dialysis, it is nanocrystalline to obtain Mierocrystalline cellulose;
Preparing the nanocrystalline method of chitin is: chitin is added the KOH aqueous solution that concentration is 40～100g/L, stirring is boiled and is boiled 6～40 hours, removes protein, filters and removes solution, obtain the chitin behind the deproteinization, every liter of KOH aqueous solution adds 20～40g chitin; Chitin after using sodium hypochlorite solution bleaching delignification protein under 60～80 ℃ 2～8 hours filters, and obtains the chitin throw out; With chitin throw out deionized water wash, 20～120 ℃ of lower dry 12～24h in vacuum drying oven, it is in the HCl solution of 2～8mol/L that chitin after the clean dry is added concentration, stirring is boiled to boil and was carried out acidolysis in 1～4 hour, obtain acid solution, the chitin after every gram clean dry adds 20～50 milliliters of HCl solution; The acid solution that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 2～6 hours, until the pH value to 5 of acid solution～7 in the dialysis tubing; Acid solution lyophilize after the dialysis, it is nanocrystalline to obtain chitin;
Described sodium hypochlorite solution is the aqueous solution of Textone and sodium acetate, and wherein the massfraction of Textone is 1～2 ﹪, and the massfraction of sodium acetate is 2～3 ﹪;
Step (2). stearic acid is added stirring and refluxing 12～36h in the sulfur oxychloride solvent, then under nitrogen protection, the sulfur oxychloride solvent is drained, obtain the stearic acid of end group chloride; Every liter of sulfur oxychloride solvent adds 10～50g stearic acid;
Step (3). the brilliant ultra-sonic dispersion of the fibrous biomass nano that makes in the step (1) in dichloromethane solvent, is joined in the stearic acid of end group chloride again, stirring and refluxing 1～3 day, it is brilliant to obtain the stearic biomass nano of surface grafting; The fibrous biomass nano crystalline substance of every gram is scattered in 10～50 milliliters of dichloromethane solvents, joins in the stearic acid of 20～50 gram end group chlorides again;
Step (4). utilize churned mechanically mode to be blended in the solution of polyvinyl resin with super-high molecular weight of swelling in the stearic biomass nano crystalline substance of surface grafting, extrude through volume pump and slot die, the 5～30s that finalizes the design in 20～60 ℃ of water-baths obtains the frozen glue film; It is brilliant to add the stearic biomass nano of 0.1～50 surface grafting that restrains in every kilogram of polyvinyl resin with super-high molecular weight;
As preferably, add the stearic biomass nano crystalline substance of 1～30 gram surface grafting in every kilogram of polyvinyl resin with super-high molecular weight;
Step (5). the frozen glue film is carried out two-way stretch, and then the extraction drying at 100～120 ℃ of lower heat setting type 30～200s, obtains ultrahigh molecular weight polyethylene/biomass nanocomposite battery diaphragm after stretching;
Described two-way stretch is that transverse and longitudinal stretches, and draw ratio is 4～10 times, 100～115 ℃ of draft temperatures.
Battery diaphragm porosity by technique of the present invention preparation is 30～55 ﹪, in length and breadth to tensile strength all greater than 200 MPa, puncture intensity is greater than 550 g, the melt fracture temperature is brought up to 155 ℃ from 145 ℃.The brilliant preparation technology of biomass nano is simple and reliable among the present invention, is fit to suitability for industrialized production; In the situation that does not change main raw material, by a small amount of nanocrystalline with adding in the resin at barrier film, under the impregnable prerequisite of other performance of lithium ion battery separator of preparation, promoted the mechanical property of barrier film, significantly improve the melt fracture temperature of UHMWPE barrier film, improved the security of lithium ion battery.
Embodiment
Below in conjunction with embodiment the present invention is done further analysis.
Fibrous biomass nano crystalline substance is that Mierocrystalline cellulose is nanocrystalline or chitin is nanocrystalline, and the specific embodiment that at first prepares fibrous biomass nano crystalline substance is:
Embodiment 1.
It is the sulphuric acid soln of 40 ﹪ that the 4g cellulose crystallite is added the 100g mass content, and 20 ℃ of lower 6h that stir add deionized water and dilute, and obtaining the nanocrystalline concentration of Mierocrystalline cellulose is the suspension of 10g/L; Suspension is centrifugal, removes supernatant liquor, will precipitate the adding deionized water and dilute, and obtains the acidic suspension that cellulose crystallite concentration is 20g/L; The acidic suspension that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 2 hours, until the pH value to 5 of acidic suspension in the dialysis tubing; Acidic suspension lyophilize after the dialysis, it is nanocrystalline to obtain Mierocrystalline cellulose.
Embodiment 2.
It is the sulphuric acid soln of 50 ﹪ that the 7g cellulose crystallite is added the 100g mass content, and 40 ℃ of lower 4h that stir add deionized water and dilute, and obtaining the nanocrystalline concentration of Mierocrystalline cellulose is the suspension of 12g/L; Suspension is centrifugal, removes supernatant liquor, will precipitate the adding deionized water and dilute, and obtains the acidic suspension that cellulose crystallite concentration is 30g/L; The acidic suspension that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 4 hours, until the pH value to 6 of acidic suspension in the dialysis tubing; Acidic suspension lyophilize after the dialysis, it is nanocrystalline to obtain Mierocrystalline cellulose.
Embodiment 3.
It is the sulphuric acid soln of 60 ﹪ that the 10g cellulose crystallite is added the 100g mass content, and 60 ℃ of lower 1h that stir add deionized water and dilute, and obtaining the nanocrystalline concentration of Mierocrystalline cellulose is the suspension of 15g/L; Suspension is centrifugal, removes supernatant liquor, will precipitate the adding deionized water and dilute, and obtains the acidic suspension that cellulose crystallite concentration is 40g/L; The acidic suspension that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 6 hours, until the pH value to 7 of acidic suspension in the dialysis tubing; Acidic suspension lyophilize after the dialysis, it is nanocrystalline to obtain Mierocrystalline cellulose.
Embodiment 4.
It is the KOH aqueous solution of 40g/L that the 20g chitin is added 1L concentration, and stirring boils boils 6 hours, removes protein, filters and removes solution, obtains the chitin behind the deproteinization; Chitin after using sodium hypochlorite solution bleaching delignification protein under 60 ℃ 8 hours filters, and obtains the chitin throw out; With chitin throw out deionized water wash, 20 ℃ of lower dry 24h in vacuum drying oven, getting chitin 10g after the clean dry, to add 200mL concentration be in the HCl solution of 8mol/L, stirring boils to boil carried out acidolysis in 1 hour, obtained acid solution; The acid solution that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 2 hours, until the pH value to 5 of acid solution in the dialysis tubing; Acid solution lyophilize after the dialysis, it is nanocrystalline to obtain chitin.
Embodiment 5.
It is the KOH aqueous solution of 70g/L that the 30g chitin is added 1L concentration, and stirring boils boils 24 hours, removes protein, filters and removes solution, obtains the chitin behind the deproteinization; Chitin after using sodium hypochlorite solution bleaching delignification protein under 70 ℃ 5 hours filters, and obtains the chitin throw out; With chitin throw out deionized water wash, 70 ℃ of lower dry 18h in vacuum drying oven, getting chitin after the 10g clean dry, to add 350mL concentration be in the HCl solution of 5mol/L, stirring boils to boil carried out acidolysis in 3 hours, obtained acid solution; The acid solution that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 4 hours, until the pH value to 6 of acid solution in the dialysis tubing; Acid solution lyophilize after the dialysis, it is nanocrystalline to obtain chitin.
Embodiment 6.
It is the KOH aqueous solution of 100g/L that the 40g chitin is added 1L concentration, and stirring boils boils 40 hours, removes protein, filters and removes solution, obtains the chitin behind the deproteinization; Chitin after using sodium hypochlorite solution bleaching delignification protein under 80 ℃ 2 hours filters, and obtains the chitin throw out; With chitin throw out deionized water wash, 120 ℃ of lower dry 12h in vacuum drying oven, getting chitin after the 10g clean dry, to add 500mL concentration be in the HCl solution of 2mol/L, stirring boils to boil carried out acidolysis in 4 hours, obtained acid solution; The acid solution that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 6 hours, until the pH value to 7 of acid solution in the dialysis tubing; Acid solution lyophilize after the dialysis, it is nanocrystalline to obtain chitin.
The embodiment I.
Step (1). the 10g stearic acid is added stirring and refluxing 12h in the 1L sulfur oxychloride solvent, then under nitrogen protection, the sulfur oxychloride solvent is drained, obtain the stearic acid of end group chloride;
Step (2). with the brilliant ultra-sonic dispersion of any one fibrous biomass nano of 1g embodiment 1～6 in the 10mL dichloromethane solvent, join again in the stearic acid of 20g end group chloride, stirring and refluxing 1 day, it is brilliant to obtain the stearic biomass nano of surface grafting;
Step (3). utilize churned mechanically mode to be blended in the solution of 1kg polyvinyl resin with super-high molecular weight of swelling in the stearic biomass nano crystalline substance of 0.1g surface grafting, extrude through volume pump and slot die, the 30s typing obtains the frozen glue film in 20 ℃ of water-baths;
Step (4). the frozen glue film that the water-bath typing is obtained carries out the transverse and longitudinal stretching, 100 ℃ of lower stretchings 4 times, then immediately extraction drying after the stretching carries out heat setting type, 100 ℃ of lower typing 200s obtain ultrahigh molecular weight polyethylene/biomass nanocomposite battery diaphragm.
The embodiment II.
Step (1). the 20g stearic acid is added stirring and refluxing 20h in the 1L sulfur oxychloride solvent, then under nitrogen protection, the sulfur oxychloride solvent is drained, obtain the stearic acid of end group chloride;
Step (2). with the brilliant ultra-sonic dispersion of any one fibrous biomass nano of 1g embodiment 1～6 in the 20mL dichloromethane solvent, join again in the stearic acid of 30g end group chloride, stirring and refluxing 1.5 days, it is brilliant to obtain the stearic biomass nano of surface grafting;
Step (3). utilize churned mechanically mode to be blended in the solution of 1kg polyvinyl resin with super-high molecular weight of swelling in the stearic biomass nano crystalline substance of 1g surface grafting, extrude through volume pump and slot die, the 20s typing obtains the frozen glue film in 30 ℃ of water-baths;
Step (4). the frozen glue film that the water-bath typing is obtained carries out the transverse and longitudinal stretching, 105 ℃ of lower stretchings 5 times, then immediately extraction drying after the stretching carries out heat setting type, 105 ℃ of lower typing 150s obtain ultrahigh molecular weight polyethylene/biomass nanocomposite battery diaphragm.
The embodiment III.
Step (1). the 30g stearic acid is added stirring and refluxing 25h in the 1L sulfur oxychloride solvent, then under nitrogen protection, the sulfur oxychloride solvent is drained, obtain the stearic acid of end group chloride;
Step (2). with the brilliant ultra-sonic dispersion of any one fibrous biomass nano of 1g embodiment 1～6 in the 30mL dichloromethane solvent, join again in the stearic acid of 35g end group chloride, stirring and refluxing 2 days, it is brilliant to obtain the stearic biomass nano of surface grafting;
Step (3). utilize churned mechanically mode to be blended in the solution of 1kg polyvinyl resin with super-high molecular weight of swelling in the stearic biomass nano crystalline substance of 20g surface grafting, extrude through volume pump and slot die, the 15s typing obtains the frozen glue film in 40 ℃ of water-baths;
Step (4). the frozen glue film that the water-bath typing is obtained carries out the transverse and longitudinal stretching, 110 ℃ of lower stretchings 7 times, then immediately extraction drying after the stretching carries out heat setting type, 110 ℃ of lower typing 100s obtain ultrahigh molecular weight polyethylene/biomass nanocomposite battery diaphragm.
The embodiment IV.
Step (1). the 40g stearic acid is added stirring and refluxing 30h in the 1L sulfur oxychloride solvent, then under nitrogen protection, the sulfur oxychloride solvent is drained, obtain the stearic acid of end group chloride;
Step (2). with the brilliant ultra-sonic dispersion of any one fibrous biomass nano of 1g embodiment 1～6 in the 40mL dichloromethane solvent, join again in the stearic acid of 40g end group chloride, stirring and refluxing 2.5 days, it is brilliant to obtain the stearic biomass nano of surface grafting;
Step (3). utilize churned mechanically mode to be blended in the solution of 1kg polyvinyl resin with super-high molecular weight of swelling in the stearic biomass nano crystalline substance of 30g surface grafting, extrude through volume pump and slot die, the 10s typing obtains the frozen glue film in 50 ℃ of water-baths;
Step (4). the frozen glue film that the water-bath typing is obtained carries out the transverse and longitudinal stretching, 112 ℃ of lower stretchings 9 times, then immediately extraction drying after the stretching carries out heat setting type, 115 ℃ of lower typing 50s obtain ultrahigh molecular weight polyethylene/biomass nanocomposite battery diaphragm.
The embodiment V.
Step (1). the 50g stearic acid is added stirring and refluxing 36h in the 1L sulfur oxychloride solvent, then under nitrogen protection, the sulfur oxychloride solvent is drained, obtain the stearic acid of end group chloride;
Step (2). with the brilliant ultra-sonic dispersion of any one fibrous biomass nano of 1g embodiment 1～6 in the 50mL dichloromethane solvent, join again in the stearic acid of 50g end group chloride, stirring and refluxing 3 days, it is brilliant to obtain the stearic biomass nano of surface grafting;
Step (3). utilize churned mechanically mode to be blended in the solution of 1kg polyvinyl resin with super-high molecular weight of swelling in the stearic biomass nano crystalline substance of 50g surface grafting, extrude through volume pump and slot die, the 5s typing obtains the frozen glue film in 60 ℃ of water-baths;
Step (4). the frozen glue film that the water-bath typing is obtained carries out the transverse and longitudinal stretching, 115 ℃ of lower stretchings 10 times, then immediately extraction drying after the stretching carries out heat setting type, 120 ℃ of lower typing 30s obtain ultrahigh molecular weight polyethylene/biomass nanocomposite battery diaphragm.
More than among each embodiment the molecular weight of polyvinyl resin with super-high molecular weight more than or equal to 5 * 10
5Sodium hypochlorite solution is the aqueous solution of Textone and sodium acetate, and wherein the massfraction of Textone is 1～2 ﹪, and the massfraction of sodium acetate is 2～3 ﹪.
Claims (4)
1. the preparation method of ultrahigh molecular weight polyethylene/biomass nanocomposite barrier film is characterized in that the method may further comprise the steps:
Step (1). it is brilliant to prepare fibrous biomass nano, and described fibrous biomass nano crystalline substance is that Mierocrystalline cellulose is nanocrystalline or chitin is nanocrystalline:
Preparing the nanocrystalline method of Mierocrystalline cellulose is: cellulose crystallite is added the sulphuric acid soln that mass content is 40～60 ﹪, wherein the mass ratio of cellulose crystallite and sulphuric acid soln is 4～10:100,20～60 ℃ of lower 1～6h that stir, add deionized water and dilute, obtaining the nanocrystalline concentration of Mierocrystalline cellulose is the suspension of 10～15g/L; Suspension is centrifugal, removes supernatant liquor, will precipitate the adding deionized water and dilute, and obtains the acidic suspension that cellulose crystallite concentration is 20～40g/L; The acidic suspension that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 2～6 hours, until the pH value to 5 of acidic suspension～7 in the dialysis tubing; Acidic suspension lyophilize after the dialysis, it is nanocrystalline to obtain Mierocrystalline cellulose;
Preparing the nanocrystalline method of chitin is: chitin is added the KOH aqueous solution that concentration is 40～100g/L, and stirring boils boils 6～40 hours, removes protein, obtains the chitin suspension behind the deproteinization; Every liter of KOH aqueous solution adds 20～40g chitin; Chitin after using sodium hypochlorite solution bleaching delignification protein under 60～80 ℃ 2～8 hours is rinsed well with deionized water, and it is in the HCl solution of 2～8mol/L that the chitin after cleaning is added concentration, and stirring boils to boil carried out acidolysis in 1～4 hour, obtained acid solution; Chitin after every gram is cleaned adds 20～50 milliliters of HCl solution; The acid solution that obtains is transferred in the dialysis tubing, in deionized water, dialysed, changed a deionized water every 2～6 hours, until the pH value to 5 of acid solution～7 in the dialysis tubing; Acid solution lyophilize after the dialysis, it is nanocrystalline to obtain chitin;
Step (2). stearic acid is added stirring and refluxing 12～36h in the sulfur oxychloride solvent, then under nitrogen protection, the sulfur oxychloride solvent is drained, obtain the stearic acid of end group chloride; Every liter of sulfur oxychloride solvent adds 10～50g stearic acid;
Step (3). the brilliant ultra-sonic dispersion of the fibrous biomass nano that makes in the step (1) in dichloromethane solvent, is joined in the stearic acid of end group chloride again, stirring and refluxing 1～3 day, it is brilliant to obtain the stearic biomass nano of surface grafting; The fibrous biomass nano crystalline substance of every gram is scattered in 10～50 milliliters of dichloromethane solvents, joins in the stearic acid of 20～50 gram end group chlorides again;
Step (4). utilize churned mechanically mode to be blended in the solution of polyvinyl resin with super-high molecular weight of swelling in the stearic biomass nano crystalline substance of surface grafting, extrude through volume pump and slot die, 5～30s typing obtains the frozen glue film in 20～60 ℃ of water-baths; It is brilliant to add the stearic biomass nano of 0.1～50 surface grafting that restrains in every kilogram of polyvinyl resin with super-high molecular weight;
Step (5). the frozen glue film that the water-bath typing is obtained carries out two-way stretch, and then immediately extraction drying after the stretching carries out heat setting type, and 100～120 ℃ of lower typing 30～200s obtain ultrahigh molecular weight polyethylene/biomass nanocomposite battery diaphragm.
2. the preparation method of ultrahigh molecular weight polyethylene/biomass nanocomposite barrier film as claimed in claim 1, it is characterized in that the described sodium hypochlorite solution of step (1) is the aqueous solution of Textone and sodium acetate, wherein the massfraction of Textone is 1～2 ﹪, and the massfraction of sodium acetate is 2～3 ﹪.
3. the preparation method of ultrahigh molecular weight polyethylene/biomass nanocomposite barrier film as claimed in claim 1 is characterized in that the described two-way stretch of step (5) is that transverse and longitudinal stretches, and draw ratio is 4～10 times, 100～115 ℃ of draft temperatures.
4. the preparation method of ultrahigh molecular weight polyethylene/biomass nanocomposite barrier film as claimed in claim 1 is characterized in that adding in every kilogram of polyvinyl resin with super-high molecular weight of step (4) the stearic biomass nano crystalline substance of 1～30 gram surface grafting.
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| CN105457494B (en) * | 2014-09-09 | 2018-02-13 | 贵阳时代沃顿科技有限公司 | A kind of nanostructured high flux seawater desalination reverse osmosis film and preparation method thereof |
| CN104993084A (en) * | 2015-05-22 | 2015-10-21 | 宁波大学 | Biomass nanocrystal coated polyolefin lithium ion battery diaphragm and production method thereof |
| CN105185940A (en) * | 2015-10-23 | 2015-12-23 | 旭成（福建）科技股份有限公司 | Preparation method and application of polyolefin/nanocrystal cellulose composite diaphragm |
| CN110265608A (en) * | 2019-06-28 | 2019-09-20 | 新乡市中科科技有限公司 | A kind of high pressure resistant lithium ion battery nano coating diaphragm and preparation method thereof |
| CN110265608B (en) * | 2019-06-28 | 2021-10-01 | 新乡市中科科技有限公司 | Nano coating diaphragm for high-voltage-resistant lithium ion battery and preparation method thereof |
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