CN111416085B - Preparation method of ultra-high molecular weight polyethylene battery diaphragm - Google Patents
Preparation method of ultra-high molecular weight polyethylene battery diaphragm Download PDFInfo
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- CN111416085B CN111416085B CN201910015276.XA CN201910015276A CN111416085B CN 111416085 B CN111416085 B CN 111416085B CN 201910015276 A CN201910015276 A CN 201910015276A CN 111416085 B CN111416085 B CN 111416085B
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 101
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 140
- 239000000758 substrate Substances 0.000 claims abstract description 56
- 238000001125 extrusion Methods 0.000 claims abstract description 49
- 238000000605 extraction Methods 0.000 claims abstract description 35
- 238000003181 co-melting Methods 0.000 claims abstract description 13
- 238000009998 heat setting Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000498 cooling water Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- -1 polyethylene Polymers 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000001502 supplementing effect Effects 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
Classifications
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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
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides a preparation method of an ultra-high molecular weight polyethylene battery diaphragm, which comprises the following steps: providing high molecular weight polyethylene, white oil A and white oil B, wherein the viscosity of the white oil A is 80-100 mm at 40 DEG C 2 S, and the viscosity of the white oil B is less than the viscosity of the white oil A; after the ultrahigh molecular weight polyethylene and the white oil A are fed, carrying out melt extrusion treatment under a heating condition to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A; the substrate is subjected to replacement-cooling treatment through a cooling roller; and (3) sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting to form a roll.
Description
Technical Field
The invention belongs to lithium ion batteries, and particularly relates to a preparation method of an ultrahigh molecular weight polyethylene battery diaphragm.
Background
Lithium ion batteries are the most competitive batteries of the new generation, are called as green energy sources, and are the first choice technology for solving the current environmental pollution problem and the energy source problem. The basic structure of a lithium ion battery includes a positive electrode, a negative electrode, and a separator disposed between the positive and negative electrodes. The separator is used for separating the positive electrode and the negative electrode of the battery and preventing the positive electrode and the negative electrode from being contacted to short-circuit. In addition, the separator serves to secure the passage of electrolyte ions. The diaphragm is used as one of the key inner layer components of the lithium ion battery, the performance of the diaphragm determines the interface structure, the internal resistance and the like of the battery, the characteristics of the battery such as capacity, circulation, safety performance and the like are directly influenced, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery. In order to ensure the performance of the lithium ion battery, the membrane material is required to have a pore canal and also required to have corresponding strength and thermal stability. Compared with common polyethylene, the ultra-high molecular weight polyethylene (the weight average molecular weight is more than 120 ten thousand) has almost zero melt fluidity, almost does not deform at 200 ℃, can better ensure the safety of the battery at high temperature, and therefore becomes a specified power battery diaphragm raw material of many battery manufacturers.
The preparation process of the diaphragm comprises extrusion, stretching, extraction, heat treatment and the like, wherein extrusion is a decisive factor. In order to ensure extrusion performance, the viscosity of the ultra-high molecular weight polyethylene and the white oil (liquid paraffin) of the two raw materials is ensured to be as similar as possible, so that the temperature adopted in general extrusion is adoptedThe temperature is 200-220 ℃. This temperature is very close to the oxidation temperature of the ultra-high molecular weight polyethylene and easily leads to degradation of the ultra-high molecular weight polyethylene. In the selection of the white oil, in order to ensure the mixing effect of the polyethylene melt and the white oil, the viscosity (40 ℃) range is generally selected to be 60-80 mm 2 And/s (the viscosity is too small to ensure the mixing effect of the polyethylene melt and the white oil), but the white oil with the viscosity range is not easy to elute in the later extraction process, so that the pore canal structure of the diaphragm is affected.
Disclosure of Invention
The invention aims to provide a preparation method of an ultrahigh molecular weight polyethylene battery diaphragm, which aims to solve the problems that white oil adopted by the existing wet diaphragm has higher viscosity, so that the ultrahigh molecular weight polyethylene with too high extrusion temperature is degraded, and the white oil is not easy to elute by extraction.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of an ultra-high molecular weight polyethylene battery diaphragm, which comprises the following steps:
providing ultra-high molecular weight polyethylene, white oil A and white oil B, wherein the viscosity of the white oil A is 80-100 mm at 40 DEG C 2 S, and the viscosity of the white oil B is less than the viscosity of the white oil A;
carrying out melt extrusion treatment, namely carrying out melt extrusion treatment on the ultrahigh molecular weight polyethylene and the white oil A after feeding treatment under a heating condition to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
the substrate is subjected to replacement-cooling treatment through a cooling roller; wherein the replacement-cooling treatment comprises a white oil B replacement treatment and a water cooling treatment, and the method for the white oil B replacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing a first cooling roller and a second cooling roller at least partially in the white oil B, extruding the molten mixture, driving the molten mixture by the first cooling roller and the second cooling roller, and replacing and primarily cooling the molten mixture in the white oil B;
and (3) sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting to form a roll.
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm provided by the invention has the viscosity of 80-100 mm at 40 DEG C 2 The white oil A with high viscosity is favorable for ensuring the mixing effect of the polyethylene melt and the white oil on the one hand; on the other hand, the white oil A has high viscosity, so that low-temperature extrusion can be realized in the extrusion process, thereby effectively preventing the degradation of the ultra-high molecular weight polyethylene and further improving the film performance. Simultaneously, in the cooling forming step, a white oil B cooling device is provided before water cooling treatment, a first cooling roller and a second cooling roller are at least partially arranged in white oil B with lower viscosity, the white oil A with higher viscosity in the ultra-high molecular weight polyethylene/white oil A mixture is replaced by driving the first cooling roller and the second cooling roller, and further, the white oil component is fully eluted in the extraction process, and further, the performance of the obtained ultra-high molecular weight polyethylene battery diaphragm is ensured.
Drawings
Fig. 1 is a schematic diagram of a white oil B cooling device according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
The embodiment of the invention provides a preparation method of an ultra-high molecular weight polyethylene battery diaphragm, which comprises the following steps:
s01, providing ultra-high molecular weight polyethylene, white oil A and white oil B, wherein the viscosity of the white oil A is 80-100 mm at 40 DEG C 2 S, and the viscosity of the white oil B is less than the viscosity of the white oil A;
s02, carrying out melt extrusion treatment on the ultrahigh molecular weight polyethylene and the white oil A under a heating condition after feeding treatment to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
s03, replacing and cooling the substrate by a cooling roller; wherein the replacement-cooling treatment comprises a white oil B replacement treatment and a water cooling treatment, and the method for the white oil B replacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing a first cooling roller and a second cooling roller at least partially in the white oil B, extruding the molten mixture, driving the molten mixture by the first cooling roller and the second cooling roller, and replacing and primarily cooling the molten mixture in the white oil B;
s04, sequentially performing longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and performing heat setting to form a roll.
The embodiment of the invention provides a preparation method of an ultra-high molecular weight polyethylene battery diaphragm, wherein the viscosity of the ultra-high molecular weight polyethylene battery diaphragm is 80-100 mm at 40 DEG C 2 The white oil A with high viscosity is favorable for ensuring the mixing effect of polyethylene melt and white oil on one hand; on the other hand, the white oil A has high viscosity, so that low-temperature extrusion can be realized in the extrusion process, thereby effectively preventing the degradation of the ultra-high molecular weight polyethylene and further improving the film performance. Simultaneously, in the cooling forming step, a white oil B cooling device is provided before water cooling treatment, a first cooling roller and a second cooling roller are at least partially arranged in the white oil B with lower viscosity, the white oil A with higher viscosity in the ultra-high molecular weight polyethylene/white oil A mixture is replaced by driving the first cooling roller and the second cooling roller, and further the white oil component is fully eluted in the extraction process, and further the obtained ultra-high molecular weight polyethylene is ensuredPerformance of the battery separator.
Specifically, in the step S01, the ultra-high molecular weight polyethylene has the advantage of having almost zero melt fluidity and hardly deforming at 200 ℃ as a matrix component of a battery separator, particularly a lithium ion battery separator. Preferably, in the embodiment of the invention, the weight average molecular weight of the ultra-high molecular weight polyethylene is 150-250 ten thousand, and the ultra-high molecular weight polyethylene in the range has the advantages of high mechanical strength, good low temperature resistance, long service life and good low temperature resistance when used as a battery diaphragm. In a particularly preferred embodiment, the ultra high molecular weight polyethylene has a weight average molecular weight of 180 ten thousand.
The white oil A is used as a pore-forming agent of the ultra-high molecular weight polyethylene in the preparation process of the wet diaphragm, is uniformly dispersed with the ultra-high molecular weight polyethylene before film formation, and is removed by extraction after film formation, and pore channels are formed at positions after the white oil A is removed in a finally obtained substrate to form electrolyte channels. Specifically, the white oil A has a viscosity of 80-100 mm at 40 DEG C 2 And/s. At this time, the temperature of the white oil A is higher, so that the mixing effect of the polyethylene melt and the white oil is guaranteed; meanwhile, the extrusion temperature in the extrusion process can be effectively reduced, so that the degradation of the ultra-high molecular weight polyethylene is effectively prevented, and the film performance is further improved.
The white oil B is a functional component added in the cooling treatment process and is used for replacing high-viscosity white oil in the ultra-high molecular weight polyethylene/white oil A mixture by the white oil B with lower viscosity. Furthermore, in the subsequent extraction process, the viscosity of the white oil B is lower, so that the white oil B is favorable for full removal, a better pore channel structure is formed, and the passing of electrolyte is facilitated; while preventing white oil residue from affecting other properties of the separator.
In the above step S02, the ultra high molecular weight polyethylene and the white oil a are fed. In some embodiments, the ultra-high molecular weight polyethylene and the white oil a may be mixed before being fed into the extruder together. In other embodiments, the melt extrusion process is performed after the ultra-high molecular weight polyethylene and the white oil a are fed separately from different feeding ports of the extruder.
In a preferred embodiment, the weight percentage of the ultra-high molecular weight polyethylene is 15% to 20% based on 100% of the total weight of the ultra-high molecular weight polyethylene and the white oil a, thereby enabling to obtain a uniform, flat and good film-layer performance substrate. If the content of the ultra-high molecular weight polyethylene is too low, the molten mixture is over-olefine, and the film forming performance is poor; if the content of the ultra-high molecular weight polyethylene is too high, the ultra-high molecular weight polyethylene is not easy to be fully and uniformly mixed, the extrusion effect is poor, unmelted ultra-high molecular weight polyethylene particles are easy to appear in the obtained film layer, the ultra-high molecular weight polyethylene particles are broken in the subsequent stretching process, and a qualified diaphragm cannot be prepared.
In the embodiment of the invention, the viscosity of the white oil A is 80-100 mm 2 As a result, at lower extrusion temperatures, the viscosity of the ultra-high molecular weight polyethylene and the white oil are relatively close to each other, and a molten homogeneous mixture is obtained. In a specific embodiment, the temperature of the extrusion treatment of the extruder is 160-190 ℃ so as to obtain a better extrusion effect. If the temperature of the extrusion treatment is too high, the ultra-high molecular weight polyethylene is easy to degrade, so that the performance of the finally obtained battery diaphragm is affected; if the temperature of the extrusion treatment is too low, it is unfavorable for sufficient melt extrusion.
Further, the rotating speed of the screw rod of the extruder is 100-300 rpm in the extrusion treatment process, so that eutectic with good shearing effect can be obtained. If the rotating speed of the screw is too high, the high polymer is degraded due to too high shearing heat of the high polymer, so that the performance of the finally obtained battery diaphragm is affected.
In the above step S03, the substrate is subjected to a substitution-cooling treatment. The embodiment of the present invention is different from the conventional cooling treatment method in that a substitution-cooling treatment is employed, and the substitution-cooling treatment includes a white oil B substitution treatment step and a water cooling treatment step. Specifically, the high-viscosity white oil A in the substrate obtained after extrusion is replaced by the low-viscosity white oil B through the white oil B replacement treatment step; and further, carrying out water cooling treatment on the white oil B after the replacement treatment, and finally obtaining the substrate.
In the embodiment of the invention, the viscosity of the white oil B is smaller than that of the white oil A, and then the white oil B can be removed by extraction after being replaced by the white oil A in the film layer, so that a pore channel structure is formed. Preferably, the viscosity of the white oil B at 40 ℃ is 40-50 mm 2 And the viscosity difference between the white oil B and the white oil A is less than 50mm 2 And/s. At this time, the white oil B has a proper viscosity and can be removed by an extractant, in particular, methylene chloride, chloroform and carbon tetrachloride; and the verified viscosity difference facilitates the displacement between white oil a and white oil B.
In a specific embodiment, the method for replacing the white oil B comprises the following steps: providing a cooling tank filled with the white oil B, and placing the first cooling roller and the second cooling roller at least partially in the white oil B to form a white oil B cooling device in a combined way, as shown in figure 1. And after the molten mixture is extruded, the molten mixture is driven by the first cooling roller and the second cooling roller to perform preliminary cooling and replacement of the white oil in the white oil B.
In the step of the white oil B replacement treatment, heat conducting oil is introduced into the first cooling roller and the second cooling roller, the temperature of the white oil B in the cooling tank is 60-80 ℃, and the temperature of the heat conducting oil of the first cooling roller and the second cooling roller is the same as the temperature of the white oil B. This temperature facilitates the initial shaping of the molten mixture and allows for efficient displacement during shaping.
The substrate which is preliminarily molded after the white oil B replacement treatment is further subjected to water cooling treatment, and preferably, the water cooling treatment method comprises the following steps: and cooling water is filled in the third cooling roller, and the substrate formed after the white oil B replacement treatment is cooled and formed by the third cooling roller.
In the embodiment of the invention, preferably, a scraper for scraping off white oil on the surface of the primary-made substrate is arranged between the second cooling roller and the third cooling roller, so that the oil content on the surface of the obtained substrate is relatively uniform, and further, the obtained substrate is heated uniformly (more places are included, the heating effect is good, and the difference between the heating effect and the stretching effect of other places is obvious) in the subsequent stretching process, thereby realizing uniform stretching.
In the step S04, the cooled substrate is sequentially subjected to longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching, and then heat-set into a roll, which can be implemented by a conventional method. Preferably, the extractant used in the extraction is at least one selected from dichloromethane, chloroform and tetrachloromethane, which is favorable for the sufficient elution of white oil B, and particularly preferably dichloromethane.
The following description is made with reference to specific embodiments.
Example 1
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
s11, providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A/s and viscosity of 50mm 2 White oil B/s;
s12, mixing the ultra-high molecular weight polyethylene and the white oil A according to the weight ratio of 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the extrusion screw speed is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
s13, carrying out replacement-cooling treatment on the molten mixture from the die head through a cooling roller; wherein the replacement-cooling treatment comprises a white oil B replacement treatment and a water cooling treatment, and the method for the white oil B replacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing a first cooling roller and a second cooling roller at least partially in the white oil B with the temperature of 80 ℃, introducing heat conduction oil into the rollers of the first cooling roller and the second cooling roller, setting the temperature of 80 ℃, extruding the molten mixture, driving the molten mixture by the first cooling roller and the second cooling roller, and replacing and primarily cooling the molten mixture in the white oil B; the water cooling treatment method comprises the following steps: cooling water is filled in the third cooling roller, and the temperature is set to be 15 ℃;
s14, sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting and rolling, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into the groove, and the fresh dichloromethane is added by 400kg/h.
Example 2
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
s21, providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A/s and viscosity of 50mm 2 White oil B/s;
s22, mixing the ultra-high molecular weight polyethylene and the white oil A according to the weight ratio of 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 195 ℃ and the extrusion screw speed is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
s23, carrying out replacement-cooling treatment on the substrate coming out of the die head through a cooling roller; wherein the replacement-cooling treatment comprises a white oil B replacement treatment and a water cooling treatment, and the method for the white oil B replacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing a first cooling roller and a second cooling roller at least partially in the white oil B with the temperature of 80 ℃, introducing heat conduction oil into the rollers of the first cooling roller and the second cooling roller, setting the temperature of 80 ℃, extruding the molten mixture, driving the molten mixture by the first cooling roller and the second cooling roller, and replacing and primarily cooling the molten mixture in the white oil B; the water cooling treatment method comprises the following steps: cooling water is filled in the third cooling roller, and the temperature is set to be 15 ℃;
s24, sequentially performing longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and performing heat setting to form a roll, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into the groove, and the fresh dichloromethane is added by 400kg/h.
Example 3
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
s31, providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A/s and viscosity50mm of 2 White oil B/s;
s32, mixing the ultra-high molecular weight polyethylene and the white oil A according to the weight ratio of 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 220 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
s33, carrying out replacement-cooling treatment on the substrate coming out of the die head through a cooling roller; wherein the replacement-cooling treatment comprises a white oil B replacement treatment and a water cooling treatment, and the method for the white oil B replacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing a first cooling roller and a second cooling roller at least partially in the white oil B with the temperature of 80 ℃, introducing heat conduction oil into the rollers of the first cooling roller and the second cooling roller, setting the temperature of 80 ℃, extruding the molten mixture, driving the molten mixture by the first cooling roller and the second cooling roller, and replacing and primarily cooling the molten mixture in the white oil B; the water cooling treatment method comprises the following steps: cooling water is filled in the third cooling roller, and the temperature is set to be 15 ℃;
s34, sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and carrying out heat setting and rolling, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into a groove, and the fresh dichloromethane is added by 400kg/h.
Comparative example 1
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
D11. providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A;
D12. the weight ratio of the ultra-high molecular weight polyethylene to the white oil A is 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the extrusion screw speed is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
D13. cooling the substrate coming out of the die head through a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting roller and a second casting roller which are internally communicated with heat conducting oil, the temperature is set to 80 ℃, and the temperature is set to 15 ℃ by the cooling water in the third casting roller;
D14. and (3) sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting and rolling, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into a groove, and the supplementing amount of fresh dichloromethane is 400kg/h.
Comparative example 2
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
D21. providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A;
D22. the weight ratio of the ultra-high molecular weight polyethylene to the white oil A is 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the extrusion screw speed is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
D23. cooling the substrate coming out of the die head through a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting roller and a second casting roller which are internally communicated with heat conducting oil, the temperature is set to 80 ℃, and the temperature is set to 15 ℃ by the cooling water in the third casting roller;
D24. and (3) sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting and rolling, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into a groove, and the supplementing amount of fresh dichloromethane is 1800kg/h.
Comparative example 3
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
D31. providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A;
D32. the weight ratio of the ultra-high molecular weight polyethylene to the white oil A is 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the extrusion screw speed is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
D33. cooling the substrate coming out of the die head through a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting roller and a second casting roller which are internally communicated with heat conducting oil, the temperature is set to 80 ℃, and the temperature is set to 15 ℃ by the cooling water in the third casting roller.
Experiments show that the film surface wrinkling phenomenon is serious because the melt viscosity is high due to the low viscosity of the white oil B.
Comparative example 4
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
D41. providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A;
D42. the weight ratio of the ultra-high molecular weight polyethylene to the white oil A is 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the extrusion screw speed is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
D43. cooling the substrate coming out of the die head through a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting roller and a second casting roller which are internally communicated with heat conducting oil, the temperature is set to 80 ℃, and the temperature is set to 15 ℃ by the cooling water in the third casting roller;
D44. and (3) sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting and rolling, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into a groove, and the supplementing amount of fresh dichloromethane is 1200kg/h.
Comparative example 5
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
D51. providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A;
D52. the weight ratio of the ultra-high molecular weight polyethylene to the white oil A is 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 220 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
D53. cooling the substrate coming out of the die head through a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting roller and a second casting roller which are internally communicated with heat conducting oil, the temperature is set to 80 ℃, and the temperature is set to 15 ℃ by the cooling water in the third casting roller;
D54. and (3) sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting and rolling, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into a groove, and the supplementing amount of fresh dichloromethane is 1200kg/h.
Comparative example 6
The preparation method of the ultra-high molecular weight polyethylene battery diaphragm comprises the following steps:
D61. providing ultra-high molecular weight polyethylene with weight average molecular weight of 180 ten thousand and viscosity of 85mm 2 White oil A;
D62. the weight ratio of the ultra-high molecular weight polyethylene to the white oil A is 1:5, after being uniformly mixed, feeding the mixture into an extruder (the total feeding amount is 300 kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 220 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultra-high molecular weight polyethylene and the white oil A;
D63. cooling the substrate coming out of the die head through a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting roller and a second casting roller which are internally communicated with heat conducting oil, the temperature is set to 80 ℃, and the temperature is set to 15 ℃ by the cooling water in the third casting roller;
D64. and (3) sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting and rolling, wherein the linear speed during extraction is 35m/min, extracting agent dichloromethane is injected into a groove, and the supplementing amount of fresh dichloromethane is 1800kg/h.
The ultra-high molecular weight polyethylene battery separators provided in examples 1-3 and comparative examples 1-6 were subjected to extraction efficiency test as follows:
(1) Taking a film sample of 10cm multiplied by 10cm at the inlet of an extraction tank, and weighing the weight m0;
(2) Removing an outlet of an extraction tank to obtain a film sample of 10cm multiplied by 10cm, and weighing the weight m1;
(3) Immersing the sample in clean dichloromethane for 3 minutes, airing, and weighing m2;
(4) Soaking the sample in clean dichloromethane for 3 minutes, airing, and weighing m3;
and so on until the mass is unchanged, denoted as mz
Extraction efficiency = (m 0-m 1)/(m 0-mz) ×100%
The test results are shown in table 1 below.
TABLE 1
From examples 1, 2 and 3, comparative examples 4 and 5, it can be seen that the higher the extrusion temperature, the lower the mechanical strength of the finished product; however, if the extrusion temperature is low, poor melting may be caused. From comparative examples 1, 2 and 4, it can be seen that the higher the viscosity of the white oil used for extrusion, the greater the amount of methylene chloride circulated.
The processing method of the ultra-high molecular weight polyethylene diaphragm generally adopts the process of the comparative example 5 at present, and compared with the comparative example 5, the processing method of the ultra-high molecular weight polyethylene diaphragm has the following advantages: 1, the product strength is high, and the degradation of polyethylene can be effectively slowed down due to the lower processing temperature; 2 the energy consumption of the process is low, 0.3-0.5 kg of steam is needed for separating 1kg of mixed solution of dichloromethane and white oil, and the circulating dichloromethane amount in the embodiment of the invention is about one third of that of the common process.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. The preparation method of the ultra-high molecular weight polyethylene battery diaphragm is characterized by comprising the following steps of:
providing ultra-high molecular weight polyethylene, white oil A and white oil B, wherein the viscosity of the white oil A is 80-100 mm at 40 DEG C 2 The viscosity of the white oil B is smaller than that of the white oil A, and the viscosity of the white oil B at 40 ℃ is 40-50 mm 2 The weight average molecular weight of the ultra-high molecular weight polyethylene is 150-250 ten thousand, and the weight percentage of the ultra-high molecular weight polyethylene is 15-20% based on the total weight of the ultra-high molecular weight polyethylene and the white oil A being 100%;
after the ultrahigh molecular weight polyethylene and the white oil A are fed, carrying out melt extrusion treatment under a heating condition to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
the substrate is subjected to replacement-cooling treatment through a cooling roller; wherein the replacement-cooling treatment comprises a white oil B replacement treatment and a water cooling treatment, and the method for the white oil B replacement treatment comprises the following steps: providing a cooling tank containing the white oil B, wherein the temperature of the white oil B in the cooling tank is 60-80 ℃, at least partially placing a first cooling roller and a second cooling roller in the white oil B, driving the molten mixture through the first cooling roller and the second cooling roller after extruding the molten mixture, and performing replacement and preliminary cooling in the white oil B, wherein the water cooling treatment method comprises the following steps: cooling water is filled in the third cooling roller, and the substrate formed after the white oil B replacement treatment is cooled and formed through the third cooling roller;
and sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching treatment on the cooled substrate, and then carrying out heat setting to form a coil.
2. The method for preparing an ultra-high molecular weight polyethylene battery separator according to claim 1, wherein the difference in viscosity between the white oil B and the white oil a is less than 50mm 2 /s。
3. The method for preparing an ultra-high molecular weight polyethylene battery separator according to claim 1, wherein the extrusion treatment temperature is 160-190 ℃.
4. The method for preparing an ultra-high molecular weight polyethylene battery separator according to claim 3, wherein the screw speed is 100-300 rpm in the extrusion treatment process.
5. The method for preparing a separator for an ultra-high molecular weight polyethylene battery according to any one of claims 1 to 4, wherein in the step of the white oil B substitution treatment, heat transfer oil is introduced into the rolls of the first and second cooling rolls, and the heat transfer oil temperature of the first and second cooling rolls is the same as the temperature of the white oil B.
6. The method for producing an ultra high molecular weight polyethylene battery separator according to any one of claims 1 to 4, wherein a doctor blade for scraping off white oil on the surface of the substrate is provided between the second cooling roll and the third cooling roll.
7. The method for preparing an ultra-high molecular weight polyethylene battery separator according to any one of claims 1 to 4, wherein the extractant used for the extraction is at least one selected from the group consisting of methylene chloride, chloroform and tetrachloromethane.
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