CN103199210A - Lithium ion battery diaphragm - Google Patents
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- CN103199210A CN103199210A CN2013101409355A CN201310140935A CN103199210A CN 103199210 A CN103199210 A CN 103199210A CN 2013101409355 A CN2013101409355 A CN 2013101409355A CN 201310140935 A CN201310140935 A CN 201310140935A CN 103199210 A CN103199210 A CN 103199210A
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Abstract
The invention discloses a lithium ion battery diaphragm. The lithium ion battery diaphragm is prepared from polyolefin and inorganic substance particles through processes of extrusion, stretching, extraction, horizontal and bidirectional stretching, thermal treatment and the like; wherein in the thermal treatment process, the heating temperature is 100-(the melting point of polyolefin+70) DEG C., the processing time is 0.5-6min, and polymers on the surface of the diaphragm are melted through ultrahigh temperature heat treatment, so that the diaphragm, the surface porosity of which is lower than the central porosity, is formed. The lithium ion battery diaphragm can not only prevent the short circuit caused by lithium crystals penetrating the diaphragm in the use of the battery, but also can ensure enough electrolyte retention rate and high battery capacity. According to the diaphragm disclosed by the invention, the entire porosity is 50-80%, the surface porosity is 20-50%, and the central porosity is 50-90%. The lithium ion battery diaphragm has good high temperature resistance performance.
Description
Technical field
The present invention relates to the lithium ion battery field, relate in particular to a kind of lithium ion battery separator.
Background technology
In the structure of lithium battery, barrier film is one of crucial interior layer assembly.The performance of barrier film has determined the interfacial structure, internal resistance of battery etc., directly influences the characteristics such as capacity, circulation and security performance of battery, and the barrier film of excellent performance has important effect to the combination property that improves battery.
The main effect of barrier film is that the positive and negative electrode of battery is separated, and prevents the two poles of the earth contacts and short circuit has the function that electrolyte ion is passed through in addition.The barrier film material is nonconducting, and its physicochemical properties have very big influence to the performance of battery.The kind difference of battery, the barrier film of employing are also different.For lithium battery series, because electrolyte is organic solvent system, thereby need have the diaphragm material of organic solvent-resistant, generally adopt the polyolefin porous membrane of high-strength thin-filmization.
At present, the polyalkene diaphragm production technology can according to dry method (fusion drawn, MSCS) and wet method (thermic is separated, and TIPS) is divided into two kinds, and simultaneously dry method can be subdivided into simple tension technology and stretch processes again.
The basic process of wet method refers at high temperature polymer to be dissolved in the solvent of higher boiling point, low volatility and forms homogeneous phase liquid, cooling cooling then, causing solution to produce liquid-solid phase separates or liquid-liquid phase separation, select for use volatile reagent that high boiling solvent is extracted again, obtain the high molecule micropore film of certain planform through super-dry.Use in the microporous barrier manufacture process at barrier film, can before solvent extraction, carry out unidirectional or biaxial tension, finalize the design after the extraction and handle and the rolling film forming, also can after extraction, stretch.
The development of battery diaphragm is to change and constantly develop along with the demand of lithium battery is continuous, especially along with the use of lithium battery in fields such as electric bicycle, electric automobile and electric tools, in order to obtain high capacity, big power to be provided, a common battery need use dozens or even hundreds of electric core to be connected in series.Because lithium battery has potential explosion hazard, the fail safe of barrier film is quite important.But no matter polyethylene, polypropylene still are other thermoplastic macromolecule materials, and material all can bring potential hidden danger for the fail safe of electrokinetic cell because of the fusing contraction distortion near fusing point the time.Domestic and international many companies and research institution all improve at barrier film thermal stability aspect.
Propose a kind of technology at polypropylene diaphragm coating PVDF in the US7794511 american documentation literature, can improve temperature tolerance to a certain extent, but because the PVDF material melting point is about 170 degree, still can not satisfy the requirement of electric automobile heatproof 200 degree;
201110002330.0 Chinese patent literature in a kind of technology at polyalkene diaphragm surface coating inorganic matter is proposed, alumina/silica/the zirconia of certain particle diameter etc. is coated membrane surface, utilize the resistance to elevated temperatures of inorganic matter to improve the temperature tolerance of barrier film integral body.But can influence the gas permeability of barrier film after the inorganic matter coating, and then the capacity of the battery that reduces finally to make, Tu Bu oxide comes off from the polyalkene diaphragm surface easily in the battery use or particles of inorganic material is fallen into the cavity of polyalkene diaphragm and caused plug-hole simultaneously, and these all can cause bad influence to the battery use.
Along with the use of lithium battery on electric automobile, the barrier film that obtains high temperature tolerance by different technological means has become an obvious development trend.But existing market is to have added a step coating process, complex process after existing barrier film production technology again in the mode of coating organic substance and inorganic matter; Though simultaneously each producer is all adopting different technology to reduce to be coated with the effect of blocking to original polyalkene diaphragm micropore, but the mode of coating has determined coating layer will inevitably block the micropore of the original barrier film of part, and the high power capacity that this and electric automobile require is runed counter to.
Summary of the invention
At above-mentioned prior art, the invention provides a kind of lithium ion battery separator, membrane surface of the present invention position is different with diaphragm center part aperture and porosity, not only can prevent battery use in the lithium crystallization penetrate barrier film and cause short circuit, but also can guarantee to have sufficiently high electrolyte conservation rate and high battery capacity.
In order to solve the problems of the technologies described above, the technical scheme that a kind of lithium ion battery separator of the present invention is achieved is: this lithium ion battery separator has following component according to ratio of quality and the number of copies and forms: 12-30 part polyolefin and 4-24 part particles of inorganic material, and its preparation method comprises following steps:
1) polyolefin, particles of inorganic material and plasticiser are joined in the double screw extruder, form homogeneous phase by adding hot shearing; Temperature is the 150-250 degree when extruding, and screw speed is at 100-600rpm;
2) mixture extruded of double screw extruder forms sheet material by hanger-style die, and to form thickness in the chill roll cooling be the thick film of 500-3000um; Chill roll is single face contact melt cooling or the cooling of two-sided contact melt, and chill-roll temperature is 0-50 ℃;
3) by the stretching of a direction or both direction, stretch ratio is 9-50 times, and thick film is drawn into film; Draft temperature is at 80-130 ℃, if the stretching of both direction, then cross directional stretch or horizontal vertical both direction stretch simultaneously behind the first longitudinal stretching;
4) film with the plasticiser flush away in the film, is lower than 1% through extraction back plasticiser residual quantity through filling with the cell body of extractant;
5) the stretched ratio of film of coming out from extraction tank is 1-2.5 cross directional stretch doubly, and the temperature of this cross directional stretch is 100-130 ℃;
6) film is heat-treated, adopt the heating of air heat or hot-rolling, heating-up temperature is 100～(polyolefin fusing point+70) ℃, processing time is 0.5-6min, film surface polymer melted after the heat treatment finally obtains the lithium ion battery separator that surface porosity factor is lower than the core porosity.
Further, above-mentioned steps 6) in, preferred heating-up temperature is (polyolefin fusing point+5)～(polyolefin fusing point+50 ℃).
By the lithium ion battery separator that preparation method of the present invention obtains, the whole porosity of its barrier film is 50-80%, and surface porosity factor is 20-50%, and the core porosity is 50-90%.
Compared with prior art, the invention has the beneficial effects as follows:
1. the product and the common polyalkene diaphragm that prepare of the present invention relatively has the very thermal endurance of high-temperature.
2. resistant to elevated temperaturesly be coated with cloth diaphragm relatively with having, the micropore hole of having avoided coating to cause tails off, the influence that battery capacity reduces.Product of the present invention has apparently higher than the porosity of coated product and battery capacity.
3. technology of the present invention mainly comprises polyalkene diaphragm preparation and coating, and it is simple for process, only is common polyolefin prepared technology is improved, and does not increase numerous and diverse processing step again, still is a step production technology.
4. the heat treatment temperature in the technical process of the present invention can realize the different of membrane surface and median pore radius and porosity, wherein, surface porosity factor is low can prevent battery use in the lithium crystallization penetrate barrier film and cause short circuit, the central porisity rate greatly then can guarantee sufficiently high electrolyte conservation rate and high battery capacity.
Description of drawings
Fig. 1 is the electron scanning micrograph of the embodiment of the invention 1;
Fig. 2 is the electron scanning micrograph of comparative example 1.
Embodiment
Below in conjunction with embodiment the present invention is done to describe in further detail.
A kind of lithium ion battery separator of the present invention is made of polyolefin and particles of inorganic material,, stretches extraction, cross directional stretch, the preparation of operations such as heat treatment by extruding.This barrier film has the high porosity of 50-80%, good resistance to elevated temperatures; And its surface porosity factor is lower than the central porisity rate.
Prepare lithium ion battery separator of the present invention and comprise following raw material:
1. polyolefin, polyolefin can be the mixtures that a kind of material or two or more polyolefin constitute.Polyolefin can be polyethylene (PE), polypropylene (PP), or contain the copolymer of alpha-alkene.Wherein preferably polyethylene can be ultra-high molecular weight polyethylene (UHMWPE) high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE) and linear low density polyethylene (LLDPE) (LLDPE).PE can be one matter, the perhaps mixture of two kinds of PE.When selecting single PE for use, preferred Mw is at the above UHMWPE of 1 * 10^6; When adopting two kinds of PE to mix, preferred MW HDPE blend in 10^4-5 * 10^5 scope at the above UHMWPE of 1 * 10^6 and Mw.
2. particles of inorganic material, particles of inorganic material can be in the sulfate of metals such as the carbonate of metals such as the nitride of metals such as the oxide of metals such as silicon, aluminium, calcium, titanium, barium and silicon, aluminium, calcium, titanium, barium or silicon, aluminium, calcium, titanium, barium and silicon, aluminium, calcium, titanium, barium one or several.Preferred silicon dioxide, alundum (Al and titanium dioxide.The preferred 1-200nm of the particle diameter of particles of inorganic material, more preferably 10-100nm.The preparation method of particles of inorganic material can be methods such as gas phase, precipitation, calcining.
3. plasticiser, plasticiser can be paraffin oil, dioctyl phthalate, dibutyl phthalate, diethyl phthalates etc. can be in the above material one or more.
4. other additives, in the scope of not damaging advantage of the present invention, as required, can with antioxidants such as phenols, sulphur class, metallic soap classes such as calcium stearate, light stabilizer, additives such as electrical static eliminator are used.
5. extractant, extractant can be hydro carbons such as n-hexane, heptane; Halogenated hydrocarbons such as carrene, trichloroethanes, trichloroethylene, ethers, hydrogen fluorine ether, alcohols such as ethanol, ketones such as acetone, butanone.
This lithium ion battery separator has following component according to ratio of quality and the number of copies and forms: 12-20 part polyolefin and 4-24 part particles of inorganic material.
The preparation technology of lithium ion battery separator of the present invention may further comprise the steps:
1) polyolefin, particles of inorganic material and plasticiser are joined in the double screw extruder, form homogeneous phase by adding hot shearing; Temperature is the 150-250 degree when extruding, and screw speed is at 100-600rpm;
2) mixture extruded of double screw extruder forms sheet material by hanger-style die, and to form thickness in the chill roll cooling be the thick film of 500-3000um; Chill roll is single face contact melt cooling or the cooling of two-sided contact melt, and chill-roll temperature is 0-50 ℃;
3) by the stretching of a direction or both direction, stretch ratio is 9-50 times, and thick film is drawn into film; Draft temperature is at 80-130 ℃, if the stretching of both direction, then cross directional stretch or horizontal vertical both direction stretch simultaneously behind the first longitudinal stretching;
4) film with the plasticiser flush away in the film, is lower than 1% through extraction back plasticiser residual quantity through filling with the cell body of extractant;
5) the stretched ratio of film of coming out from extraction tank is 1-2.5 cross directional stretch doubly, and the temperature of this cross directional stretch is 100-130 ℃;
6) film is heat-treated, adopt the heating of air heat or hot-rolling, heating-up temperature is 100～(polyolefin fusing point+70) ℃, this heating-up temperature is preferably (polyolefin fusing point+5)～(polyolefin fusing point+50 ℃), processing time is 0.5-6min, and the film surface polymer melted after the heat treatment finally obtains surface porosity factor and is lower than the core porosity, be that surface porosity factor is 20-50%, the core porosity is the lithium ion battery separator of 50-90%.(
The characteristics of lithium ion battery separator of the present invention are: surface porosity factor is little, and the central porisity rate is big; The little porosity in surface can prevent battery use in the lithium crystallization penetrate barrier film and cause short circuit, the central porisity rate can guarantee sufficiently high electrolyte conservation rate and high battery capacity greatly.
Tell about detailed process of the present invention by the following examples, it is convenience in order to understand that embodiment is provided, and never is restriction the present invention.
Be 1,000,000 ultra-high molecular weight polyethylene, the silicon dioxide of 10 parts of particle diameter 50nm with 20 parts of molecular weight, 70 parts of paraffin oils are extruded by double screw extruder, and extrusion temperature is 220 ℃, and chill-roll temperature is 25 ℃, obtains the thick film of thickness 1000um.Enter biaxial orientation stretching machine and longitudinally and laterally respectively stretch 7 times, draft temperature is 120 ℃.Film after the stretching enters in the heptane groove, stops 10min.Enter the cross directional stretch machine after the extraction, bounce back to 1.05 times then along 1.2 times of cross directional stretch, the cross directional stretch temperature is 130 ℃.Finally by the heat treatment of crossing the two sides hot-rolling, heat roller temperature is 150 ℃, processing time 6min.
Embodiment 2
Change biaxial tension ratio among the embodiment 1 into 5 * 5 times, all the other are identical with embodiment 1.
Embodiment 3
Change heat treatment temperature among the embodiment 1 into 130 ℃, all the other are identical with embodiment 1.
Embodiment 4
Be 1,000,000 ultra-high molecular weight polyethylene, the silicon dioxide of 15 parts of particle diameter 50nm with 15 parts of molecular weight, 70 parts of paraffin oils are extruded by double screw extruder, and extrusion temperature is 230 ℃, and chill-roll temperature is 5 ℃.All the other are identical with embodiment 1.
Embodiment 5
Be 1,000,000 ultra-high molecular weight polyethylene, the silicon dioxide of 24 parts of particle diameter 50nm with 12 parts of molecular weight, 64 parts of paraffin oils are extruded by double screw extruder, and extrusion temperature is 250 ℃, and chill-roll temperature is 5 ℃, obtains the thick film of thickness 2000um.Enter biaxial orientation stretching machine and longitudinally and laterally respectively stretch 7 times, draft temperature is 120 ℃.Film after the stretching enters in the heptane groove, stops 10min.Enter the cross directional stretch machine after the extraction, bounce back to 1.05 times then along 1.2 times of cross directional stretch, the cross directional stretch temperature is 130 ℃.Finally by the heat treatment of crossing the two sides hot-rolling, heat roller temperature is 180 ℃, processing time 3min.
Embodiment 6
Be that 1,000,000 ultra-high molecular weight polyethylene, 18 parts of molecular weight are 300,000 high density polyethylene (HDPE) with 8 parts of molecular weight, 4 parts of melt index are 2 polypropylene, the silicon dioxide of 4 parts of particle diameter 50nm, 66 parts of paraffin oils are extruded by double screw extruder, extrusion temperature is 200 ℃, chill-roll temperature is 50 ℃, obtains the thick film of thickness 2000um.Enter biaxial orientation stretching machine and longitudinally and laterally respectively stretch 7 times, draft temperature is 105 ℃.Film after the stretching enters in the heptane groove, stops 10min.Enter the cross directional stretch machine after the extraction, bounce back to 1.05 times then along 1.2 times of cross directional stretch, the cross directional stretch temperature is 133 ℃.Finally by the heat treatment of crossing the two sides hot-rolling, heat roller temperature is 150 ℃, processing time 3min.
Embodiment 7
Be that 1,000,000 ultra-high molecular weight polyethylene, 20 parts of molecular weight are 300,000 high density polyethylene (HDPE) with 8 parts of molecular weight, the aluminium oxide of 10 parts of particle diameter 100nm, 62 parts of paraffin oils are extruded by double screw extruder, and extrusion temperature is 220 ℃, chill-roll temperature is 40 ℃, obtains the thick film of thickness 500um.Enter biaxial orientation stretching machine and longitudinally and laterally respectively stretch 5 times, draft temperature is 125 ℃.Film after the stretching enters in the butanone groove, stops 10min.Enter the cross directional stretch machine after the extraction, bounce back to 1.05 times then along 1.1 times of cross directional stretch, the cross directional stretch temperature is 133 ℃.Finally by the heat treatment of crossing the two sides hot-rolling, heat roller temperature is 160 ℃, processing time 1min.
Embodiment 8
Be 500,000 high density polyethylene (HDPE) with 30 parts of molecular weight, the calcium carbonate of 8 parts of particle diameter 200nm, 62 parts of paraffin oils are extruded by double screw extruder, and extrusion temperature is 180 ℃, and chill-roll temperature is 5 ℃, obtains the thick film of thickness 2000um.Enter biaxial orientation stretching machine and longitudinally and laterally respectively stretch 5 times, draft temperature is 90 ℃.Film after the stretching enters in the heptane groove, stops 10min.Enter the cross directional stretch machine after the extraction, bounce back to 1.05 times then along 1.2 times of cross directional stretch, the cross directional stretch temperature is 131 ℃.Finally by the heat treatment of crossing the two sides hot-rolling, heat roller temperature is 150 ℃, processing time 6min.
Embodiment 9
Be 500,000 high density polyethylene (HDPE) with 20 parts of molecular weight, the titanium dioxide of 10 parts of particle diameter 15nm, 70 parts of paraffin oils, 0.5 part antioxidant tertiary butyl hydroquinones is extruded by double screw extruder, extrusion temperature is 200 ℃, chill-roll temperature is 5 ℃, obtains the thick film of thickness 2000um.Enter biaxial orientation stretching machine and longitudinally and laterally respectively stretch 7 times, draft temperature is 110 ℃.Film after the stretching enters in the heptane groove, stops 10min.Enter the cross directional stretch machine after the extraction, bounce back to 1.05 times then along 1.2 times of cross directional stretch, the cross directional stretch temperature is 131 ℃.Finally by the heat treatment of crossing the two sides hot-rolling, heat roller temperature is 170 ℃, processing time 6min.
Comparative example 1
Be 1,000,000 ultra-high molecular weight polyethylene with 20 parts of molecular weight, 80 parts of paraffin oils are extruded by double screw extruder, and extrusion temperature is 210 ℃, and chill-roll temperature is 25 ℃, obtains the thick film of thickness 1600um.Enter biaxial orientation stretching machine and longitudinally and laterally respectively stretch 7 times, draft temperature is 120 ℃.Film after the stretching enters in the heptane groove, stops 10min.Enter the cross directional stretch machine after the extraction, bounce back to 1.05 times then along 1.2 times of cross directional stretch, the cross directional stretch temperature is 130 ℃.Finally by the heat treatment of crossing the two sides hot-rolling, heat roller temperature is 130 ℃, processing time 6min.
Comparative example 2
Barrier film coating one deck inorganic matter with comparative example 1.
PVDF-CTFE with 10% is dissolved in the acetone, and dispersed with stirring 12h forms the homogeneous slurries.With SiO
2Particle joins in the established slurries, stirs 12h, forms slurries (SiO
2Addition control is at PVDF-CTFE:SiO
2=1:2).Be coated on the barrier film both sides of comparative example 1 with dip coating, coating layer thickness is single face 3um.
For the characteristics that prove absolutely that lithium ion battery separator of the present invention has, to test at the following aspects respectively for above-described embodiment and Comparative Examples, its test result is as shown in following table, and project and the condition of its test are as follows:
1. the test of thickness: adopt calibrator under 25 ℃, to test.
2. the test of porosity: barrier film is cut into the disk that diameter is 47mm, goes out volume according to surface area and THICKNESS CALCULATION, weigh quality with assay balance.
Porosity (%)=(volume-quality/barrier film raw material density)/volume * 100
Barrier film raw material density for according to and alkene and inorganic matter proportioning and the averag density calculated of densitometer separately, in plasticiser is not included in.
3. the test of air permeability: Gurley air permeability instrument is tested certain gas flow by the required time of barrier film.
4. the test of puncture intensity: adopt universal testing machine, the syringe needle radius of curvature is 0.5mm.
5. the test of shrinkage: square barrier film is put into baking oven, 105 ℃ or 150 ℃ of temperature, time 1h.The change calculations of measuring length on the both direction goes out shrinkage.
Shrinkage (%)=(original length-baking back length)/original length * 100
Compare the embodiment of the invention 1 and comparative example 2 as can be seen, the whole porosity of embodiment 1 is 70%, but from electron scanning micrograph, surface porosity factor is not high as can be seen; Comparative example 1 porosity is 42% can see that from electron micrograph surface porosity factor is higher than embodiment 1.It is low to be that barrier film of the present invention has a surface porosity factor, the feature that the central porisity rate is high.
In a word, the barrier film that the present invention makes is compared with conventional polyalkene diaphragm (comparative example 1), and porosity and air permeability exceed a lot, must bring capacity high in the battery; The while thermal contraction performance, especially 150 ℃ of thermal contraction performances obviously are better than comparative example 1.The barrier film that the present invention makes is compared with being coated with cloth diaphragm (comparative example 2), and thermal contraction performance also improves a lot, and it is a lot of that while porosity and air permeability are higher than comparative example 2.
Although top invention has been described in conjunction with figure; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; rather than it is restrictive; those of ordinary skill in the art is under enlightenment of the present invention; under the situation that does not break away from aim of the present invention, can also make a lot of distortion, these all belong within the protection of the present invention.
Claims (10)
1. lithium ion battery separator has following component according to ratio of quality and the number of copies and forms: 12-30 part polyolefin and 4-24 part particles of inorganic material, and its preparation method comprises following steps:
1) polyolefin, particles of inorganic material and plasticiser are joined in the double screw extruder, form homogeneous phase by adding hot shearing; Temperature is the 150-250 degree when extruding, and screw speed is at 100-600rpm;
2) mixture extruded of double screw extruder forms sheet material by hanger-style die, and to form thickness in the chill roll cooling be the thick film of 500-3000um; Chill roll is single face contact melt cooling or the cooling of two-sided contact melt, and chill-roll temperature is 0-50 ℃;
3) by the stretching of a direction or both direction, stretch ratio is 9-50 times, and thick film is drawn into film; Draft temperature is at 80-130 ℃, if the stretching of both direction, then cross directional stretch or horizontal vertical both direction stretch simultaneously behind the first longitudinal stretching;
4) film with the plasticiser flush away in the film, is lower than 1% through extraction back plasticiser residual quantity through filling with the cell body of extractant;
5) the stretched ratio of film of coming out from extraction tank is 1-2.5 cross directional stretch doubly, and the temperature of this cross directional stretch is 100-130 ℃;
6) film is heat-treated, adopt the heating of air heat or hot-rolling, heating-up temperature is 100～(polyolefin fusing point+70) ℃, processing time is 0.5-6min, film surface polymer melted after the heat treatment finally obtains the lithium ion battery separator that surface porosity factor is lower than the core porosity.
2. according to the described lithium ion battery separator of claim 1, it is characterized in that the whole porosity of barrier film is 50-80%, and surface porosity factor is 20-50%, the core porosity is 50-90%.
3. according to the described lithium ion battery separator of claim 1, it is characterized in that polyolefin is the mixture that a kind of material or two or more polyolefin constitute.
4. according to the described lithium ion battery separator of claim 1, it is characterized in that polyolefin is polyethylene (PE), polypropylene (PP), or contain the copolymer of alpha-alkene.
5. according to the described lithium ion battery separator of claim 4, it is characterized in that, described polyethylene is ultra-high molecular weight polyethylene (UHMWPE), high density polyethylene (HDPE) (HDPE), any in low density polyethylene (LDPE) (LDPE) and the linear low density polyethylene (LLDPE) (LLDPE).
6. according to the described lithium ion battery separator of claim 5, it is characterized in that described polyethylene is the mixture of single polyethylene material or two kinds of polythene PEs; If during single polyethylene, adopt Mw at the above ultra-high molecular weight polyethylene UHMWPE of 1 * 10^6; If during two kinds of poly mixtures, adopt MW high density polyethylene blend in 10^4-5 * 10^5 scope at the above ultra-high molecular weight polyethylene UHMWPE of 1 * 10^6 and Mw.
7. according to the described lithium ion battery separator of claim 1, it is characterized in that, particles of inorganic material is the oxide of silicon, aluminium, calcium, titanium and barium, the nitride of silicon, aluminium, calcium, titanium and barium, the carbonate of silicon, aluminium, calcium, titanium and barium, in the sulfate of silicon, aluminium, calcium, titanium and barium one or several, the particle diameter of particles of inorganic material are 1-200nm; The preparation method of particles of inorganic material is any method in gas phase, precipitation and the calcining.
8. according to the described lithium ion battery separator of claim 7, it is characterized in that particles of inorganic material is one or more in silicon dioxide, alundum (Al and the titanium dioxide, the particle diameter of particles of inorganic material is 10-100nm.
9. according to the described lithium ion battery separator of claim 1, it is characterized in that the draft temperature in the step 3) is 90-125 ℃, take the stretching of both direction, stretch ratio is 5 * 5 or 7 * 7 biaxial tensiones.
10. according to the described lithium ion battery separator of claim 1, it is characterized in that in the step 6), heating-up temperature is (polyolefin fusing point+5)～(polyolefin fusing point+50 ℃).
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| CN103700796A (en) * | 2013-12-05 | 2014-04-02 | 宁波华丰包装有限公司 | Preparation method of lithium ion diaphragm |
| CN106252563A (en) * | 2016-08-31 | 2016-12-21 | 河南义腾新能源科技有限公司 | A kind of lithium ion battery separator and preparation method thereof |
| CN108550769A (en) * | 2018-05-21 | 2018-09-18 | 珠海光宇电池有限公司 | The preparation method and lithium ion battery of lithium ion battery separator |
| CN108832064A (en) * | 2018-06-26 | 2018-11-16 | 河北金力新能源科技股份有限公司 | A kind of composite ceramic porous lithium electric separator, preparation method and applications |
| CN110931688A (en) * | 2019-12-13 | 2020-03-27 | 重庆云天化纽米科技股份有限公司 | Highly extended polyolefin separator and applications |
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| CN112290165A (en) * | 2020-11-05 | 2021-01-29 | 青岛蓝科途膜材料有限公司 | Lithium ion battery diaphragm, preparation method and lithium ion battery |
| CN113451706A (en) * | 2018-07-17 | 2021-09-28 | 河南义腾新能源科技有限公司 | Polyethylene diaphragm for lithium ion battery and preparation method thereof |
| CN113451707A (en) * | 2020-03-26 | 2021-09-28 | 溧阳月泉电能源有限公司 | Polyolefin diaphragm and preparation method thereof |
| CN113972435A (en) * | 2021-09-26 | 2022-01-25 | 中材锂膜有限公司 | Preparation method of high-porosity and high-permeability lithium ion battery base membrane |
| CN114843705A (en) * | 2022-05-16 | 2022-08-02 | 武汉中原长江科技发展有限公司 | Lithium metal battery diaphragm and preparation method and application thereof |
| CN116396547A (en) * | 2023-04-10 | 2023-07-07 | 安徽九牛塑业科技有限公司 | Porous plastic film material and preparation method thereof |
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| CN113451706A (en) * | 2018-07-17 | 2021-09-28 | 河南义腾新能源科技有限公司 | Polyethylene diaphragm for lithium ion battery and preparation method thereof |
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| CN111040215A (en) * | 2019-12-30 | 2020-04-21 | 江苏厚生新能源科技有限公司 | Method for controlling pore size distribution and size of diaphragm by changing crystal structure of UHMWPE material |
| CN113451707A (en) * | 2020-03-26 | 2021-09-28 | 溧阳月泉电能源有限公司 | Polyolefin diaphragm and preparation method thereof |
| CN112290165A (en) * | 2020-11-05 | 2021-01-29 | 青岛蓝科途膜材料有限公司 | Lithium ion battery diaphragm, preparation method and lithium ion battery |
| CN113972435A (en) * | 2021-09-26 | 2022-01-25 | 中材锂膜有限公司 | Preparation method of high-porosity and high-permeability lithium ion battery base membrane |
| WO2023045384A1 (en) * | 2021-09-26 | 2023-03-30 | 中材锂膜有限公司 | High-porosity, high-permeability lithium ion battery base film and preparation method therefor, and lithium ion battery |
| CN114843705A (en) * | 2022-05-16 | 2022-08-02 | 武汉中原长江科技发展有限公司 | Lithium metal battery diaphragm and preparation method and application thereof |
| CN116396547A (en) * | 2023-04-10 | 2023-07-07 | 安徽九牛塑业科技有限公司 | Porous plastic film material and preparation method thereof |
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