CN101645498A - Method for regulating and controlling formation of polyolefin microporous membrane and method for forming lithium cell separator - Google Patents
Method for regulating and controlling formation of polyolefin microporous membrane and method for forming lithium cell separator Download PDFInfo
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Abstract
The invention provides a method for regulating and controlling the formation of polyolefin microporous membrane, comprising the following steps: regulating heat treatment condition of polyolefin basemembrane, and generating metastable phase of the polyolefin base membrane in the heat treatment course; utilizing a differential scanning calorimeter (DSC) to monitor metastable phases of the polyolefin base membrane generated in each heat treatment course; monitoring the performance of micropore formed by each metastable phase of the polyolefin base membrane; and regulating and controlling the micropore formation of the polyolefin base membrane according to the monitored metastable phases of the polyolefin base membrane and the micropore performance. The invention also provides a method for forming a lithium cell separator. In the regulating and controlling method, by means of analysis of the DSC, the invention monitors the formation of metastable phase and the influence of performance thereof on the final formation of the micropore, so as to obtain metastable phase structures of the polyolefin base membrane corresponding to the polyolefin base membranes with different microporous performances, thereby being capable of regulating and controlling the formation of the polyolefin base membranes by regulating heat treatment condition and being applicable to the manufacturing of lithium cell separators with various aperture requirements.
Description
Technical field
The present invention relates to polyolefin base membrane manufacturing technology field, be specifically related to a kind of regulate and control the method that microporous polyolefin film forms and the formation method of lithium battery diaphragm.
Background technology
Polyolefin base membrane can form microcellular structure, is commonly used for the barrier film of lithium ion battery, and for lithium ion battery, different application requires lithium ion batteries to lay particular emphasis on different electric properties, and it is good etc. to reach cyclicity greatly as high-multiplying power discharge, memory capacity.To the lithium ion battery that different electric properties require, its requirement to barrier film is also different.This just requires barrier film also should customize production accordingly.
Microporous polyolefin film mainly adopts thermally induced phase separation and two kinds of method productions of pulling method at present.Thermally induced phase separation is owing to adopt the organic solvent extracting access method in film-forming process, equipment investment is big, cost is high, returns environmental protection and safety in production simultaneously and all will bring big pressure.And the basic principle of pulling method to be basement membrane after polyolefin is melt extruded just obtain microporous barrier through unidirectional or biaxial tension, invest little, cost is lower, and whole process non-pollutant discharge.
Pulling method prepares microporous barrier and mainly contains two kinds of implementation methods: a kind of is that density changes and crystalline region defective generation micropore when utilizing the polyolefin crystal transfer.There are defectives such as the aperture is little, pore-size distribution is uneven, porosity is low, ventilative difference in the microporous barrier that this method makes, and is also less at present as lithium battery diaphragm.Another kind is that polyolefin melt is extruded the basement membrane that obtains having the hard elastics characteristic through Overheating Treatment, and basement membrane is stretched more promptly to make microporous barrier with thermal finalization.Utilize this method to realize the suitability for industrialized production lithium ion battery separator at present.
As mentioned above, for satisfying the requirement of lithium ion battery on different electric properties, make barrier film also require to customize accordingly production.Have numerous advantages such as environmental protection, cost be low though pulling method prepares microporous barrier, it exists complex process, aperture and distribution thereof to be difficult to control, can't satisfy the customization production of barrier film, thereby stop the extensive use of this class barrier film.At present, utilize pulling method to prepare aperture and the complete controlled sizable difficulty that for barrier film manufacturer, also has of porosity, therefore how seeking a kind of aperture and complete controlled barrier film monitoring method and production method of porosity of realizing and have very important significance, also is simultaneously the key point that enlarges the lithium ion battery applications field.
Summary of the invention
In view of this, be necessary to provide a kind of regulate and control the method that microporous polyolefin film forms and the formation method of lithium battery diaphragm, this method is implemented easily, can effectively be regulated aperture and porosity, realizes the customization production of polyolefin base membrane and lithium battery diaphragm.
A kind ofly regulate and control the method that microporous polyolefin film forms, it comprises the steps:
Regulate the polyolefin base membrane heat-treat condition, in heat treatment process, produce the metastable phase of polyolefin base membrane;
Utilize difference formula scanning calorimeter to monitor the polyolefin base membrane metastable phase that produces in each heat treatment process; And
Monitor the performance of the micropore that each polyolefin base membrane metastable phase forms, regulate and control the formation of polyolefin-based microporous barrier according to the polyolefin base membrane metastable phase that monitors and micropore performance.
And, a kind of formation method of lithium battery diaphragm, it comprises the steps:
Polyolefin base membrane is heat-treated, and the micropore of regulating and control polyolefin base membrane according to the method for above-mentioned regulation and control microporous polyolefin film formation forms, and obtains to possess the presoma of required micropore performance;
Heat treated presoma is carried out stretch processing, make to change into the extended chain crystalline phase that presents microporous barrier behind the presoma drawn; And
Presoma after stretching is carried out thermal finalization, obtain the controlled lithium battery diaphragm of micropore.
In said method, monitor the polyolefin base membrane metastable phase by difference formula scanning calorimeter, monitor the corresponding micropore performance that forms of each polyolefin base membrane metastable phase simultaneously, regulate and control the formation of polyolefin base membrane according to monitoring result, this method mainly is by means of difference formula scanning calorimeter analysis means, the influence that the formation of monitoring metastable phase and performance thereof form last micropore, obtain forming the pairing polyolefin base membrane metastable phase of the polyolefin base membrane structure of different micropore performances, thereby can be by regulating the micropore formation that heat-treat condition is regulated and control polyolefin base membrane, with the lithium battery diaphragm of the required micropore performance of further acquisition.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is the method flow diagram that the regulation and control microporous polyolefin film of the embodiment of the invention forms;
Fig. 2 is the poor formula scanning calorimeter spectrogram (hereinafter to be referred as DSC figure) of typical polyolefin base membrane;
Fig. 3 is the DSC figure of a kind of polyolefin base membrane metastable phase after the heat treatment in the method that forms of the regulation and control microporous polyolefin film of the embodiment of the invention;
Fig. 4 is the DSC figure of the another kind of polyolefin base membrane metastable phase after the heat treatment in the method that forms of the regulation and control microporous polyolefin film of the embodiment of the invention;
Fig. 5 is the formation method flow diagram of the lithium battery diaphragm of the embodiment of the invention;
Fig. 6 is the DSC figure of the microporous polyolefin film that obtains of the method for the embodiment of the invention; And
Fig. 7 is the sem photograph (hereinafter to be referred as SEM figure) of the microporous polyolefin film that obtains of the method for the embodiment of the invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, the method that the regulation and control microporous polyolefin film of the embodiment of the invention forms comprises the steps:
S01: regulate the polyolefin base membrane heat-treat condition, in heat treatment process, produce the metastable phase of polyolefin base membrane;
S02: utilize difference formula scanning calorimeter to monitor the polyolefin base membrane metastable phase that produces in each heat treatment process; And
S03: monitor the performance of the micropore that each polyolefin base membrane metastable phase forms, regulate and control the formation of microporous polyolefin film according to the polyolefin base membrane metastable phase that monitors and micropore performance.
In the polyolefin base membrane heat treatment process, can improve its amorphous fraction structure and eliminate the crystalline portion defective, obtain a kind of hard elastics presoma like this.Because in heat treatment process, the crystalline texture of basement membrane changes, and forms a metastable phase between crystalline region and amorphous area, thereby this hard elastics presoma polyolefin base membrane that is a kind of metastable phase.Wherein, heat-treat condition comprises heat treated temperature and/or time, thereby, regulate the polyolefin base membrane heat-treat condition and just regulate heat treated temperature and/or time, present embodiment is regulated heat treated temperature and time respectively, by changing heat treated temperature and time, obtain the polyolefin base membrane of different metastable phases.
The polyolefin of polyolefin base membrane is selected from least a in polyethylene, polypropylene, poly-1-butylene, poly-1-amylene and the poly(4-methyl-1-pentene).Present embodiment is an example with the polyethylene, and for polyethylene, its heat treatment temperature is at 60-130 ℃, and optimum temperature is 80-110 ℃, and heat treatment time is 10 seconds to 10 hours, and the best is 5-60 minute.In another embodiment of polypropylene material, heat treatment temperature is 80-160 ℃, and optimum temperature is 90-150 ℃.Heat treatment time is 20 seconds to 10 hours, and the best is 1-60 minute.Wherein heat treatment temperature can reach in advance design temperature by programmed temperature method.
The DSC figure of the polyolefin base membrane that stable crystalline phase is intact as shown in Figure 2, usually has a tangible peak, there is not other assorted peak, the crystalline phase that this polyolefin base membrane is described is single, do not have non crystalline structure and crystal defect to exist, do not have metastable phase, this DSC figure can record after regulation and control, so that compare, with the peak type feature of the DSC figure that highlights metastable phase with the DSC figure of metastable phase.
Shown in Fig. 3 and 4, two kinds of DSC figure of the polyolefin base membrane metastable phase that forms for heat treatment process, after Overheating Treatment, different heat-treat conditions all will be reflected among the DSC figure.In this DSC figure, remove the main peak part that characterizes the conventional crystalline phase of polyolefin base membrane, also have a submaximum, it appears at before the heat treatment temperature, and this submaximum is micro-protuberance slightly, and this submaximum characterizes the existence of polyolefin base membrane metastable phase.Present embodiment is monitored this metastable phase peak, comprises the position and/or the peak area size of monitoring this metastable phase peak, and present embodiment is monitored the position and the peak area at metastable phase peak simultaneously, and the position at metastable phase peak mainly is the change in location with respect to main peak.Can regulate and control the micropore performance of microporous polyolefin film during concrete the monitoring by the position of comparing relatively stable crystalline phase peak, metastable phase peak.For example, by regulating aperture size and the pore-size distribution that close main peak in metastable phase peak and metastable phase peak area size are regulated and control micropore, with the micropore performance of regulation and control microporous polyolefin film.In Fig. 3, the metastable phase peak is comparatively mild, and peak area is less, and the metastable phase peak among Fig. 4 is comparatively steep and sharp, and peak area is bigger, and the metastable phase peak position among two figure is similar, all apart from main peak about about 35 ℃.The polyolefin base membrane metastable phase, promptly the hard elastics presoma is controllable, for example can control by heat-treat condition such as temperature and time.For example, in high heat treatment temperature, the metastable phase peak is walked on high temperature.
After monitoring corresponding metastable phase peak feature by DSC, monitor the performance of the micropore that each polyolefin base membrane metastable phase forms again.The micropore performance comprises at least one in porosity, permeability, aperture size and the pore-size distribution of micropore, by these micropore performances are monitored and controlled, with the formation of regulation and control microporous polyolefin film.The monitoring result of present embodiment shows that the position at metastable phase peak and peak area are for the size and the distribution decisive role of follow-up micropore.Present embodiment is by the monitoring at this metastable phase peak being regulated and control formation and the pore size and the distribution etc. of micropore.With the polyethylene is example, and the monitoring result of present embodiment shows that the metastable phase peak is obvious more, and the aperture of micropore is big more, and pore-size distribution is narrow and even.And the metastable phase peak is the closer to main peak, and the aperture of the micropore of Xing Chenging is big more at last, and pore-size distribution is narrow and even, therefore can obtain more equally distributed micropore size by regulation and control metastable phase peak near main peak.In other polyolefin kind, also can obtain the metastable phase peak to the micropore Effect on Performance by above-mentioned steps, for example can be the peak area at metastable phase peak and position and micropore size size and distribute between have specific relation or rule, the micropore of regulating and control this kind microporous polyolefin film by this relation or rule forms again.Certainly, be understandable that, in some polyolefin kind, might not have obviously specific relation or rule between the peak area at metastable phase peak and position and micropore size size and the distribution, but, different pore sizes and pore-size distribution all can be reflected on the peak area and position at metastable phase peak, have certain mapping relations, as meet certain function curve relation.Therefore, present embodiment forms with the micropore that reaches regulation and control kind of microporous polyolefin film by the peak area and the position at monitoring metastable phase peak.
Actual when forming polyolefin-based membrane micropore, can require specific micropore size, pass through said method, monitor the metastable phase peak performance and the heat-treat condition of required micropore size correspondence, thereby realize the aperture is regulated and control, the method for present embodiment can reach more accurate homogeneity range to the distribution in aperture, for example, adopt the regulate and control method of present embodiment,, can reach the polyolefin base membrane of aperture in 0.2-0.3 micron close limit like this by regulating heat-treat condition.In the present embodiment, modulated polyolefin-based film thickness is in the 10-200 micron, and the aperture size of modulated polyolefin-based membrane micropore is in the 0.05-0.4 micron, and porosity is in the 30-80% scope.
See also Fig. 5, the formation method of the lithium battery diaphragm of the embodiment of the invention comprises the steps:
S11: polyolefin base membrane is heat-treated, and the micropore of regulating and control polyolefin base membrane according to the method for above-mentioned regulation and control microporous polyolefin film formation forms, and obtains to possess the presoma of required micropore performance;
S12: heat treated presoma is carried out stretch processing, make to change into the extended chain crystalline phase that presents microporous barrier behind the presoma drawn; And
S13: the presoma after stretching is carried out thermal finalization, obtain the controlled lithium battery diaphragm of micropore.
S11 promptly comprises aforesaid each step S01-S03 and corresponding control methods etc., does not repeat them here.During stretching, comprise cold drawn and hot-drawn, particularly, heat treated presoma through cold drawn 1.05-1.6 doubly hot-drawn 1.1-6.0 times, just can make required microporous barrier through thermal finalization at last.DSC after the stretching can be clearly seen that as shown in Figure 6 the metastable phase peak that forms is converted into the brilliant peak of the extended chain that presents microporous barrier fully in heat treatment process, its peak value promptly is visible as bimodal on DSC figure near 170 ℃.The lithium battery diaphragm that makes at last can be used as but be not limited to lithium ion battery separator, and following examples are example with the lithium ion battery separator.
The prepared microporous barrier thickness range of present embodiment method is at 10-200 μ m.For example, utilize the prepared 25 μ m lithium ion battery separators of present embodiment method, air penetrability is that 15-40s/10ml is controlled, and porosity is controlled at 30-80%, and thermal contraction was carried out 2 hours less than 2.5% in following 1 hour at 105 ℃ under 4%, 90 ℃.Utilize the lithium ion battery separator of the prepared 40 μ m of present embodiment method, air penetrability is that 40-80s/10ml is controlled, and porosity is controlled at 30-80%, and 105 ℃ of thermal contractions were carried out 2 hours less than 2.5% in following 1 hour under 4%, 90 ℃.
The ESEM of the prepared microporous polyolefin film of the embodiment of the invention (SEM) photo as shown in Figure 7, as seen from the figure, its pore diameter range is between 0.05-0.4 μ m, and wherein most of aperture is between 0.2-0.4 μ m, whole pore-size distribution meets normal distribution, and is more even relatively.
Below illustrate the micropore performance of formed lithium ion battery separator under the Different Heat Treatment Conditions by a plurality of embodiment.
Embodiment one
With polyethylene (PE) basement membrane 70 ℃ of following heat treatments 10 minutes, cold drawn then 1.1 times, 4.0 times of 100 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its thickness is 19 μ m, and ventilative is 25s/10ml, and porosity is 37%, 90 ℃ of thermal contraction 1.5% in following 2 hours.
Embodiment two
With polyethylene (PE) basement membrane 125 ℃ of following heat treatments 10 minutes, cold drawn then 1.1 times, 4.0 times of 100 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 20 μ m, and ventilative is 19s/10ml, and porosity is 44%, 90 ℃ of thermal contraction 1.8% in following 2 hours.
Embodiment three
With polyethylene (PE) basement membrane 90 ℃ of following heat treatments 1 minute, cold drawn then 1.1 times, 4.0 times of 100 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 20 μ m, and ventilative is 17s/10ml, and porosity is 46%, 90 ℃ of thermal contraction 2.0% in following 2 hours.
Embodiment four
With polyethylene (PE) basement membrane 90 ℃ of following heat treatments 8 hours, cold drawn then 1.1 times, 4.0 times of 100 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 19 μ m, and ventilative is 14s/10ml, and porosity is 53%, 90 ℃ of thermal contraction 2.3% in following 2 hours.
Embodiment five
With the 90 ℃ of following heat treatment 30 seconds under 10N tension force condition of polyethylene (PE) basement membrane, cold drawn then 1.1 times, 4.0 times of 100 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 20 μ m, and ventilative is 16s/10ml, and porosity is 48%, 90 ℃ of thermal contraction 2.2% in following 2 hours.
Embodiment six
With polypropylene (PP) basement membrane 110 ℃ of following heat treatments 10 minutes, cold drawn then 1.4 times, 4.5 times of 110 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 25 μ m, and ventilative is 38s/10ml, and porosity is 37%, 90 ℃ of thermal contraction 1.3% in following 2 hours.
Embodiment seven
With polypropylene (PP) basement membrane 150 ℃ of following heat treatments 10 minutes, cold drawn then 1.4 times, 4.5 times of 110 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 25 μ m, and ventilative is 34s/10ml, and porosity is 41%, 90 ℃ of thermal contraction 1.8% in following 2 hours.
Embodiment eight
With polypropylene (PP) basement membrane 110 ℃ of following heat treatments 30 seconds, cold drawn then 1.4 times, 4.5 times of 110 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 25 μ m, and ventilative is 32s/10ml, and porosity is 44%, 90 ℃ of thermal contraction 1.7% in following 2 hours.
Embodiment nine
With polypropylene (PP) basement membrane 110 ℃ of following heat treatments 10 hours, cold drawn then 1.4 times, 4.5 times of 110 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 24 μ m, and ventilative is 28s/10ml, and porosity is 61%, 90 ℃ of thermal contraction 2.5% in following 2 hours.
Embodiment ten
With the 110 ℃ of following heat treatment 10 seconds under 15N tension force of polypropylene (PP) basement membrane, cold drawn then 1.4 times, 4.5 times of 110 ℃ of hot-drawns, after obtain microporous barrier after the thermal finalization.Surveying its its thickness is 24 μ m, and ventilative is 28s/10ml, and porosity is 61%, 90 ℃ of thermal contraction 2.5% in following 2 hours.
The foregoing description one to five is experiments that the polyvinyl membrane micropore is formed, and the result shows, under the heat-treat condition of these embodiment, breathes freely in the scope of 14-25s/10ml, and porosity is in the scope of 37-53%, and thermal contraction is in the scope of 1.5-2.3%.Embodiment six to ten is experiments that the polypropylene-base membrane micropore is formed, and the result shows, under the heat-treat condition of these embodiment, breathes freely in the scope of 28-38s/10ml, and porosity is in the scope of 37-61%, and thermal contraction is in the scope of 1.3-2.5%.Show that by these data by regulating and control suitable heat-treat condition, microporous barrier shows micropore performance comparatively uniformly, thereby realize the micropore of microporous barrier is formed.
In the formation method of method that above-mentioned regulation and control microporous polyolefin film forms and lithium ion battery separator, monitor the polyolefin base membrane metastable phase by difference formula scanning calorimeter, monitor the corresponding micropore performance that forms of each polyolefin base membrane metastable phase simultaneously, regulate and control the formation of polyolefin base membrane according to monitoring result, this method mainly is by means of difference formula scanning calorimeter analysis means, the influence that the formation of monitoring metastable phase and performance thereof form last micropore, obtain forming the pairing polyolefin base membrane metastable phase of the polyolefin base membrane structure of different micropore performances, thereby can be by regulating the micropore formation that heat-treat condition is regulated and control polyolefin base membrane, with the lithium ion battery separator of the required micropore performance of further acquisition.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1, a kind ofly regulates and control the method that microporous polyolefin film forms, it is characterized in that, comprise the steps:
Regulate the polyolefin base membrane heat-treat condition, in heat treatment process, produce the metastable phase of polyolefin base membrane;
Utilize difference formula scanning calorimeter to monitor the polyolefin base membrane metastable phase that produces in each heat treatment process; And
Monitor the performance of the micropore that each polyolefin base membrane metastable phase forms, regulate and control the formation of microporous polyolefin film according to the polyolefin base membrane metastable phase that monitors and micropore performance.
2, the method for regulation and control microporous polyolefin film formation as claimed in claim 1, it is characterized in that, described micropore performance comprises at least one in porosity, permeability, aperture size and the pore-size distribution of micropore, and the described regulation and control that microporous polyolefin film is formed comprise aperture size and the pore-size distribution of regulating and control micropore.
3, the method that forms of regulation and control microporous polyolefin film as claimed in claim 1 is characterized in that, the polyolefin of described polyolefin base membrane is selected from least a in polyethylene, polypropylene, poly-1-butylene, poly-1-amylene and the poly(4-methyl-1-pentene).
4, the method for regulation and control microporous polyolefin film formation as claimed in claim 1 is characterized in that, the step of described adjusting polyolefin base membrane heat-treat condition comprises regulates polyolefin base membrane heat treatment temperature and/or time.
5, the method that forms of regulation and control microporous polyolefin film as claimed in claim 1 is characterized in that, the monitoring of described polyolefin base membrane metastable phase comprises the position and/or the area at the metastable phase peak that monitoring is recorded by difference formula scanning calorimeter.
6, the method for regulation and control microporous polyolefin film formation as claimed in claim 5, it is characterized in that, described poor formula scanning calorimeter further records the stable crystalline phase main peak of polyolefin base membrane, regulates and control the micropore performance of microporous polyolefin film by the position of comparing the relatively stable crystalline phase main peak in metastable phase peak.
7, the method for regulation and control microporous polyolefin film formation as claimed in claim 6, it is characterized in that, by regulating aperture size and the pore-size distribution that close main peak in metastable phase peak and metastable phase peak area size are regulated and control micropore, with the micropore performance of regulation and control microporous polyolefin film.
8, the method for regulation and control microporous polyolefin film formation as claimed in claim 1 is characterized in that described modulated polyolefin-based film thickness is in the 10-200 micron.
9, the method that forms of regulation and control microporous polyolefin film as claimed in claim 1 is characterized in that, the aperture size of described modulated microporous polyolefin film is in the 0.05-0.4 micron, and porosity is in the 30-80% scope, and the aperture after regulation and control is normal distribution.
10, a kind of formation method of lithium battery diaphragm is characterized in that, comprises the steps:
Polyolefin base membrane is heat-treated, and the micropore of regulating and control polyolefin base membrane according to the method that forms as each described regulation and control microporous polyolefin film of claim 1-9 forms, and obtains to possess the presoma of required micropore performance;
Heat treated presoma is carried out stretch processing, make to change into the extended chain crystalline phase that presents microporous barrier behind the presoma drawn; And
Presoma after stretching is carried out thermal finalization, obtain the controlled lithium battery diaphragm of micropore.
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| CN101954738A (en) * | 2010-09-16 | 2011-01-26 | 湖南紫皇冠新能源技术服务有限公司 | Method for preparing polymer microporous membrane for lithium ion battery |
| CN102153771A (en) * | 2010-11-12 | 2011-08-17 | 深圳市星源材质科技股份有限公司 | Polyolefin microporous membrane preparation method and use |
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| CN101954738A (en) * | 2010-09-16 | 2011-01-26 | 湖南紫皇冠新能源技术服务有限公司 | Method for preparing polymer microporous membrane for lithium ion battery |
| CN102153771A (en) * | 2010-11-12 | 2011-08-17 | 深圳市星源材质科技股份有限公司 | Polyolefin microporous membrane preparation method and use |
| CN102153771B (en) * | 2010-11-12 | 2012-10-31 | 深圳市星源材质科技股份有限公司 | Polyolefin microporous membrane preparation method and use |
| CN105810870A (en) * | 2016-05-24 | 2016-07-27 | 深圳市新技术研究院有限公司 | Battery membrane and preparation method thereof, battery and application of 1-butenyl polymer in battery membrane |
| CN106252564A (en) * | 2016-09-06 | 2016-12-21 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of high puncture strength lithium ion battery separator |
| CN110416470A (en) * | 2019-08-07 | 2019-11-05 | 江苏厚生新能源科技有限公司 | The improved method of battery diaphragm and its preparation process, reduction methylene chloride consumption |
| CN110416470B (en) * | 2019-08-07 | 2022-03-11 | 江苏厚生新能源科技有限公司 | Battery diaphragm, preparation process thereof and improved method for reducing consumption of dichloromethane |
| CN111098533A (en) * | 2019-12-31 | 2020-05-05 | 武汉中兴创新材料技术有限公司 | Preparation method of hard elastic polypropylene film, hard elastic polypropylene film and application |
| 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 |
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