CN108183190B - Pore-forming agent removing method of battery diaphragm and preparation process of lithium ion secondary battery diaphragm - Google Patents
Pore-forming agent removing method of battery diaphragm and preparation process of lithium ion secondary battery diaphragm Download PDFInfo
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- CN108183190B CN108183190B CN201711430523.XA CN201711430523A CN108183190B CN 108183190 B CN108183190 B CN 108183190B CN 201711430523 A CN201711430523 A CN 201711430523A CN 108183190 B CN108183190 B CN 108183190B
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- 238000000034 method Methods 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 58
- 238000002137 ultrasound extraction Methods 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims description 26
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003361 porogen Substances 0.000 claims 4
- 238000000605 extraction Methods 0.000 abstract description 30
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000035699 permeability Effects 0.000 description 7
- 238000007790 scraping Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a pore-forming agent removing method of a battery diaphragm and a preparation process of a lithium ion secondary battery diaphragm, wherein the pore-forming agent removing method of the battery diaphragm comprises the following steps: pretreating the diaphragm substrate through equipment, and removing at least a part of pore-forming agent in the diaphragm substrate in advance; and extracting the pretreated diaphragm substrate by ultrasonic extraction to extract the pore-forming agent, and ensuring that the residual rate of the pore-forming agent of the finally prepared battery diaphragm is lower than 1%. The invention improves the extraction speed of the battery diaphragm without increasing the length of the battery production line and improving the equipment precision and the personnel skill, is particularly suitable for extracting thicker diaphragm substrates, and solves the problem of difficult extraction of the thicker substrates.
Description
Technical Field
The invention relates to a pore-forming agent removing method of a battery diaphragm and a preparation process of a lithium ion secondary battery diaphragm.
Background
At present, lithium ion secondary batteries are increasingly widely used in the fields of consumer electronics, electric vehicles and energy storage due to their high energy density and long cycle life. With more and more diaphragm production lines put into production, the competition among diaphragm enterprises is more and more intense. Currently, most enterprises increase the number of production lines to increase the yield. No technical innovation, large investment and long period. Once the predetermined goal is not reached, significant losses will result.
In the BOPP industry, the produced film is a non-porous film, and a pore-forming agent is not required to be added into the film and extracted out, so that the speed of the production line can reach 500m/min, and the width can reach 10 m.
The production technology of the current diaphragm is that the diaphragm is stretched and then extracted, so that the extraction speed is difficult to increase, and the speed of a production line is restricted to be increased greatly. The difficulty points are as follows: firstly, the extraction speed is accelerated, the length of a production line is increased, and the equipment investment is increased; secondly, the extraction speed is accelerated, the operation difficulty is increased, and the requirements on the skill of personnel and the precision of equipment are higher. Thirdly, the extraction speed is accelerated, and a large amount of solvent is brought out, thereby causing appearance problems such as film surface mottle, stripes and the like.
The process of first extraction and then stretching is introduced in the eleventh 762 page of the molding processing of the Danzhibose in Japan, but the process has not been realized industrially, mainly because the prior substrate is thick (0.7-2mm), the extraction is difficult, and the industrial production is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for removing a pore-forming agent of a battery diaphragm, which improves the extraction speed of the battery diaphragm under the conditions of not increasing the length of a battery production line and not improving the precision of equipment and personnel skills, is particularly suitable for extracting a thicker diaphragm substrate and solves the problem of difficult extraction of the thicker substrate.
In order to solve the technical problems, the technical scheme of the invention is as follows: a method for removing pore-forming agent of battery diaphragm is applied to the preparation process of lithium ion secondary battery diaphragm, and the method comprises the following steps:
pretreating the diaphragm substrate through equipment, and removing at least a part of pore-forming agent in the diaphragm substrate in advance;
and extracting the pretreated diaphragm substrate by ultrasonic extraction to extract the pore-forming agent, and ensuring that the residual rate of the pore-forming agent of the finally prepared battery diaphragm is lower than 1%.
Further, in order to improve the extraction efficiency of the diaphragm substrate better, in the ultrasonic extraction process, the ultrasonic frequency is 17KHz-28KHz, and the ultrasonic extraction time is more than 10 min.
Further provided is a concrete structure of an apparatus for pretreating a membrane substrate so as to be able to remove a part of a pore-forming agent in the membrane substrate, the apparatus comprising a squeegee roller group apparatus having at least one pair of squeegee rollers and a vacuum adsorption apparatus having at least one vacuum adsorption roller, the pretreatment comprising pretreatment of the membrane substrate by the squeegee roller group and pretreatment of the membrane substrate by the vacuum adsorption roller.
Furthermore, the pore-forming agent and the extracting agent adopted in the ultrasonic extraction process are mutually soluble organic solvents.
Further, the thickness of the diaphragm substrate is 0.7 mm-2 mm.
Further, the pore-forming agent is white oil.
Further, in order to better reduce the preparation time of the lithium ion secondary battery diaphragm and accelerate the extraction efficiency of the diaphragm substrate, the preparation process of the lithium ion secondary battery diaphragm comprises the following steps: and a biaxial stretching process, wherein the pore-forming agent removing method is positioned before the biaxial stretching process.
The invention also provides a preparation process of the lithium ion secondary battery diaphragm, which comprises the following steps:
(a) extruding and cooling to form a diaphragm substrate;
(b) the pore-forming agent removing method is adopted;
(c) then carrying out biaxial tension;
(d) and then the lithium ion secondary battery diaphragm with a stable pore structure is formed after heat treatment.
Further provides a specific step (a), wherein the step (a) is specifically as follows: mixing polyethylene and a pore-forming agent according to the required mass percentage of each component, adding the mixture into a double-screw extruder, fully melting, extruding the molten melt through a die head of the double-screw extruder, and forming a diaphragm substrate on a cooling roller; wherein, the mass percent of the polyethylene is 15% -50%; the balance being pore formers, totaling 100%.
Further provides a specific step (c), wherein the step (c) is specifically as follows: stretching the diaphragm substrate processed in the step (b) in the transverse direction and the longitudinal direction at 120 ℃; wherein the stretching ratio in stretching is 4 to 9 times.
Further, in order to make the pore-forming agent not volatile during extrusion melting and volatilize the extracting agent during heat treatment to form a stable pore structure, the boiling point temperature of the pore-forming agent is higher than the highest melting temperature during extrusion in the step (a), and the boiling point temperature of the extracting agent adopted during ultrasonic extraction is lower than the highest temperature during heat treatment in the step (d).
After the technical scheme is adopted, in the technical process of preparing the diaphragm, the procedures of biaxial tension and ultrasonic extraction are exchanged, the diaphragm substrate is scraped and pressed by the scraping roller group before ultrasonic extraction, and the diaphragm substrate can be adsorbed by the vacuum adsorption roller, so that a part of pore-forming agent in the diaphragm substrate can be removed in advance, the proportion of the pore-forming agent removed is about 10 percent approximately, then the diaphragm substrate can enter an extraction tank provided with an ultrasonic device, the pore-forming agent is extracted by controlling the intensity and the frequency of ultrasonic waves, and the residual rate of the pore-forming agent of the finally prepared battery diaphragm is ensured to be lower than 1 percent, thereby effectively shortening the extraction time and accelerating the extraction rate, and achieving the aim of high-speed production, the diaphragm substrate containing the pore-forming agent is pretreated by the scraping roller group and the vacuum adsorption roller, and is added with the ultrasonic waves of 17kHz-28kHz, the extraction time of the substrate can be shortened from 90min to 10min, and the problem of difficult extraction of a thick substrate (0.7 mm-2 mm) is effectively solved.
Drawings
Fig. 1 is a schematic structural view of a part of the apparatus in the pore-forming agent removing method for a battery separator according to the present invention.
Detailed Description
In order that the present invention may be more readily and clearly understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings.
Example one
A method for removing pore-forming agent of battery diaphragm is applied to the preparation process of lithium ion secondary battery diaphragm, and the method comprises the following steps:
pretreating the diaphragm substrate through equipment, and removing at least a part of pore-forming agent in the diaphragm substrate in advance; in the present embodiment, the pore-forming agent is white oil, but is not limited thereto; the white oil has kinematic viscosity of 45-55mm at 40 deg.C2/s；
And extracting the pretreated diaphragm substrate by ultrasonic extraction to extract the pore-forming agent, and ensuring that the residual rate of the pore-forming agent of the finally prepared battery diaphragm is lower than 1%.
In the ultrasonic extraction process, the ultrasonic frequency is 17KHz, and the ultrasonic extraction time is 10 min.
The device comprises a scraping roller set device with at least one pair of scraping roller sets 1 and a vacuum adsorption device with at least one vacuum adsorption roller 2, wherein the pretreatment comprises the steps of pretreating the diaphragm substrate through the scraping roller sets 1 and pretreating the diaphragm substrate through the vacuum adsorption roller 2, and after the pretreatment, the pore-forming agent removing rate of the scraping roller sets 1 and the vacuum adsorption roller 2 is 10% by weighing the weight change of the diaphragm substrate;
the pore-forming agent and the extracting agent adopted in the ultrasonic extraction process are mutually soluble organic solvents.
The thickness of the diaphragm substrate in this embodiment is 1 mm.
The preparation process of the lithium ion secondary battery diaphragm comprises the following steps: and a biaxial stretching process, wherein the pore-forming agent removing method is positioned before the biaxial stretching process.
A preparation process of a lithium ion secondary battery diaphragm applies the pore-forming agent removing method of the battery diaphragm of the embodiment, and the steps of the preparation process comprise:
(a) extruding and cooling to form a diaphragm substrate;
(b) a pore-forming agent removing method is adopted;
(c) then carrying out biaxial tension;
(d) and then the lithium ion secondary battery diaphragm with a stable pore structure is formed after heat treatment.
The step (a) is specifically as follows: mixing polyethylene and a pore-forming agent according to the required mass percentage of each component, adding the mixture into a double-screw extruder, fully melting the mixture at 195 ℃, extruding the molten melt through a die head of the double-screw extruder, and forming a diaphragm substrate with the thickness of 1mm on a cooling roller at 25 ℃; wherein, the mass percent of the polyethylene is 30%, the molecular weight of the polyethylene is 80 ten thousand, the molecular weight of the polyethylene can be 30 ten thousand to 350 ten thousand, and is preferably 30 ten thousand to 250 ten thousand; the pore-forming agent is white oil, and the mass percent of the pore-forming agent is 70 percent; in this embodiment, the mass percentages of the polyethylene and the pore-forming agent are respectively: 30% and 70%, but not limited thereto, the mass percentages of polyethylene and pore former may also be: 15% and 85%; can also be 50% and 50% respectively; the mass percentage of the polyethylene can be selected between 15% and 50%.
The step (c) is specifically as follows: stretching the diaphragm substrate treated in the step (b) at 120 ℃ by 5 times in the transverse direction and the longitudinal direction; of course, the stretch ratio in stretching may be selected from 4 to 9 times, and is not limited to 5 times stretching.
The boiling point temperature of the pore-forming agent is higher than the highest melting temperature during the extrusion in the step (a), and the boiling point temperature of an extracting agent adopted in the ultrasonic extraction process is lower than the highest temperature during the heat treatment in the step (d); in the embodiment, the boiling point temperature of the pore-forming agent is higher than 210 ℃, and the highest melting temperature during extrusion is 195 ℃; the maximum temperature in the heat treatment in the step (d) was 130 ℃.
In the cleaning principle of the ultrasonic device 4 of this embodiment, the transducer converts sound energy into mechanical energy, so that the cleaning liquid in the extraction tank 3 vibrates to generate a large amount of bubbles. When the sound pressure or intensity is applied to a certain degree, the bubble expands rapidly and then closes suddenly. In the process, shock waves are generated at the moment of closing the bubbles, so that 1012-1013pa pressure and local temperature regulation are generated around the bubbles, and the huge pressure generated by the ultrasonic cavitation can destroy insoluble dirt to enable the insoluble dirt to be differentiated into the solution, so that the extraction efficiency can be effectively improved and the extraction time can be shortened by adopting the ultrasonic extraction diaphragm substrate.
Example two
This embodiment is substantially the same as the first embodiment, except that: in the ultrasonic extraction process, the ultrasonic frequency is 28KHz, and the ultrasonic extraction time is 10 min.
EXAMPLE III
This embodiment is substantially the same as the first embodiment, except that: in the ultrasonic extraction process, the ultrasonic frequency is 17KHz, and the ultrasonic extraction time is 15 min.
Comparative example 1
This embodiment is substantially the same as the first embodiment, except that: in the embodiment, ultrasonic extraction is not adopted, a conventional extraction mode is adopted, and the extraction time is 10min in the extraction process.
Comparative example II
This embodiment is substantially the same as the first embodiment, except that: in the ultrasonic extraction process, the ultrasonic frequency is 120KHz, and the ultrasonic extraction time is 10 min.
Comparative example III
This embodiment is substantially the same as the first embodiment, except that: in the ultrasonic extraction process, the ultrasonic frequency is 17KHz, and the ultrasonic extraction time is 5 min.
The evaluation of the extraction effect of the above examples and comparative examples is generally characterized by the residual rate of the pore-forming agent and the air permeability Gurley value;
the smaller the residual rate of the pore-forming agent is, the better the extraction effect is; the lower the Gurley value of the film, the better the air permeability characteristic of the film.
The acquisition method of the residual rate of the pore-forming agent comprises the following steps: cutting 10cm × 10cm heat-treated diaphragm substrate, weighing m by electronic balance1Extracting the membrane substrate, taking out, air drying in a fume hood, and weighing the membrane substrate again2The pore former residue ratio of the separator substrate is then: (m)1-m2)/m1。
The method for acquiring the ventilation value comprises the following steps: the Gurley test is used to test the time required for 100ml of air to pass through a diaphragm substrate having a circular cross-sectional area of 1 inch.
The influence of the residual rate of the pore-forming agent on the permeability of the film is generally as follows
| Residual ratio of pore-forming agent (%) | 3.4 | 2.1 | 0.8 | 0.4 |
| Air permeability value (s/100ml) | 485 | 367 | 216 | 204 |
When the residual rate of the pore-forming agent is less than 1%, the air permeability value of the microporous membrane is less than 300s/100ml, and the characteristic of the diaphragm substrate is qualified.
The pore former residue and permeability values collected in the above examples and comparative examples are shown in the following table:
| example one | Example two | EXAMPLE III | Comparative example 1 | Comparative example II | Comparative example III | |
| Residual ratio of pore-forming agent (%) | 0.79 | 0.87 | 0.18 | 0.41 | 1.81 | 1.58 |
| Air permeability value (s/100ml) | 236 | 243 | 221 | 227 | 437 | 412 |
It can be seen from the above examples and comparative examples that, after the membrane substrate containing the pore-forming agent is pretreated by the scraper roll group 1 and the vacuum adsorption roll 2, the extraction time of the membrane substrate can be shortened and the problem of difficult extraction of the thick substrate can be solved by ultrasonic extraction, when 17kHz-28kHz ultrasonic wave is added, the extraction time of the membrane substrate is reduced to more than 10min, the extraction effect is excellent, and the interval is the optimal frequency range and the optimal extraction time of the ultrasonic wave parameters.
The above embodiments are described in further detail to solve the technical problems, technical solutions and advantages of the present invention, and it should be understood that the above embodiments are only examples of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for removing pore-forming agent of battery diaphragm is applied to the preparation process of lithium ion secondary battery diaphragm, and is characterized in that the preparation process of the lithium ion secondary battery diaphragm comprises the following steps: the method comprises a biaxial stretching process, wherein a pore-forming agent removing method is positioned before the biaxial stretching process, and the method comprises the following steps:
pretreating the diaphragm substrate through equipment, and removing at least a part of pore-forming agent in the diaphragm substrate in advance;
extracting the pretreated diaphragm substrate by ultrasonic extraction to extract the pore-forming agent, and ensuring that the residual rate of the pore-forming agent of the finally prepared battery diaphragm is lower than 1%; wherein,
the device comprises a scraper roller group device with at least one pair of scraper roller groups (1) and a vacuum adsorption device with at least one vacuum adsorption roller (2), and the pretreatment comprises pretreatment of the membrane substrate through the scraper roller groups (1) and pretreatment of the membrane substrate through the vacuum adsorption roller (2).
2. The porogen removal method of claim 1, wherein: in the ultrasonic extraction process, the ultrasonic frequency is 17KHz-28KHz, and the ultrasonic extraction time is more than 10 min.
3. The porogen removal method of claim 1, wherein: the pore-forming agent and the extracting agent adopted in the ultrasonic extraction process are mutually soluble organic solvents.
4. The porogen removal method of claim 1, wherein: the thickness of the diaphragm substrate is 0.7 mm-2 mm.
5. A preparation process of a lithium ion secondary battery diaphragm is characterized by comprising the following steps:
(a) extruding and cooling to form a diaphragm substrate;
(b) using the porogen removal process of any one of claims 1 to 4;
(c) then carrying out biaxial tension;
(d) and then the lithium ion secondary battery diaphragm with a stable pore structure is formed after heat treatment.
6. The process according to claim 5, characterized in that: the step (a) is specifically as follows: mixing polyethylene and a pore-forming agent according to the required mass percentage of each component, adding the mixture into a double-screw extruder, fully melting, extruding the molten melt through a die head of the double-screw extruder, and forming a diaphragm substrate on a cooling roller; wherein, the mass percent of the polyethylene is 15% -50%; the balance being pore formers, totaling 100%.
7. The process according to claim 5, characterized in that: the step (c) is specifically as follows: stretching the diaphragm substrate processed in the step (b) in the transverse direction and the longitudinal direction at 120 ℃; wherein the stretching ratio in stretching is 4 to 9 times.
8. The process according to claim 5, characterized in that: the boiling point temperature of the pore-forming agent is higher than the highest melting temperature during the extrusion in the step (a), and the boiling point temperature of the extracting agent adopted in the ultrasonic extraction process is lower than the highest temperature during the heat treatment in the step (d).
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| CN111081948A (en) * | 2019-12-26 | 2020-04-28 | 江苏厚生新能源科技有限公司 | Preparation method of high linear velocity-large width polyethylene diaphragm |
| CN112439224A (en) * | 2020-09-29 | 2021-03-05 | 河北金力新能源科技股份有限公司 | Diaphragm extraction system |
| CN112864528B (en) * | 2021-04-26 | 2021-07-13 | 江苏厚生新能源科技有限公司 | Biaxial tension coating microporous diaphragm for lithium ion battery and preparation method thereof |
| CN113871791B (en) * | 2021-08-25 | 2023-07-07 | 江西省通瑞新能源科技发展有限公司 | High-pressure-resistance diaphragm for lithium ion battery and preparation method thereof |
| CN114851506B (en) * | 2022-07-07 | 2022-10-25 | 溧阳月泉电能源有限公司 | Manufacturing process of lithium battery polyolefin diaphragm |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252756A (en) * | 1979-06-27 | 1981-02-24 | General Motors Corporation | Process for manufacturing ultra-thin sintered PVC battery separators |
| CN106450112A (en) * | 2016-11-25 | 2017-02-22 | 上海恩捷新材料科技股份有限公司 | Battery isolating membrane preparation method |
| CN106531930A (en) * | 2016-10-28 | 2017-03-22 | 深圳瑞隆新能源科技有限公司 | Paraffin oil-containing wet diaphragm production process |
-
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- 2017-12-26 CN CN201711430523.XA patent/CN108183190B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252756A (en) * | 1979-06-27 | 1981-02-24 | General Motors Corporation | Process for manufacturing ultra-thin sintered PVC battery separators |
| CN106531930A (en) * | 2016-10-28 | 2017-03-22 | 深圳瑞隆新能源科技有限公司 | Paraffin oil-containing wet diaphragm production process |
| CN106450112A (en) * | 2016-11-25 | 2017-02-22 | 上海恩捷新材料科技股份有限公司 | Battery isolating membrane preparation method |
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Effective date of registration: 20211207 Address after: 611500 No. 420, Tianlai 1st Road, new energy and new material industry functional zone, Tianfu new area, Qionglai City, Chengdu City, Sichuan Province Patentee after: Sichuan zhuoqin New Material Technology Co.,Ltd. Address before: 213300 no.619, wharf West Street, Liyang City, Changzhou City, Jiangsu Province Patentee before: LIYANG TNS ELECTRO-ENERGY Co.,Ltd. |