CN111416085A - 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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- CN111416085A CN111416085A CN201910015276.XA CN201910015276A CN111416085A CN 111416085 A CN111416085 A CN 111416085A CN 201910015276 A CN201910015276 A CN 201910015276A CN 111416085 A CN111416085 A CN 111416085A
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 104
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 141
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 238000001125 extrusion Methods 0.000 claims abstract description 49
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 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 41
- 239000000203 mixture Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 18
- 238000006073 displacement reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000498 cooling water Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 23
- 238000005266 casting Methods 0.000 description 18
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000013589 supplement Substances 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000002349 favourable effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 230000009286 beneficial effect Effects 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
- 239000000047 product Substances 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
- 238000002791 soaking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- 230000007613 environmental effect Effects 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
- 230000008570 general process Effects 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
- 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
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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
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 the temperature of 40 DEG C2(ii) 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 the heating condition to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A; performing replacement-cooling treatment on the substrate by using 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 and coiling.
Description
Technical Field
The invention belongs to a lithium ion battery, and particularly relates to a preparation method of an ultrahigh molecular weight polyethylene battery diaphragm.
Background
The lithium ion battery is the most competitive battery of the new generation, is called as the green environmental protection energy, and is the first choice technology for solving the current environmental pollution problem and the energy 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 diaphragm is used for separating the positive electrode and the negative electrode of the battery and preventing the positive electrode and the negative electrode from contacting and being short-circuited. 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 separator material is required to have a pore channel and also needs to have corresponding strength and thermal stability. Compared with common polyethylene, the ultra-high molecular weight polyethylene (with the weight-average molecular weight of more than 120 ten thousand) has almost zero melt flowability and hardly deforms at 200 ℃, so that the battery safety at high temperature can be better guaranteed, and the ultra-high molecular weight polyethylene becomes a raw material of a power battery diaphragm appointed by many battery manufacturers.
The preparation process of the diaphragm comprises extrusion, stretching, extraction, heat treatment and the like, wherein the extrusion is a decisive factor. In order to ensure the extrusion performance, the viscosities of the two raw materials, namely the ultra-high molecular weight polyethylene and the white oil (liquid paraffin), are required to be ensured to be as close as possible, so that the temperature selected for extrusion is generally 200-220 ℃. This temperature is very close to the oxidation temperature of ultra-high molecular weight polyethylene, which easily leads to degradation of 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 ℃) is generally selected to be 60-80 mm2And/s (viscosity is too small to ensure the mixing effect of the polyethylene melt and the white oil), but the white oil in the viscosity range is not easy to elute in the later extraction process, so that the pore structure of the diaphragm is influenced.
Disclosure of Invention
The invention aims to provide a preparation method of an ultrahigh molecular weight polyethylene battery diaphragm, and aims to solve the problems that the extrusion temperature is too high, the ultrahigh molecular weight polyethylene is degraded, and the white oil is not easy to elute through extraction due to the high viscosity of the white oil adopted by the existing wet diaphragm.
In order to achieve the 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 ultrahigh molecular weight polyethylene, white oil A and white oil B, wherein the viscosity of the white oil A is 80-100 mm at the temperature of 40 DEG C2(ii) and the viscosity of the white oil B is less than the viscosity of the white oil a;
performing melt extrusion treatment, namely performing melt extrusion treatment under the heating condition after feeding treatment of the ultrahigh molecular weight polyethylene and the white oil A to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
performing replacement-cooling treatment on the substrate by using a cooling roller; the displacement-cooling treatment comprises white oil B displacement treatment and water cooling treatment, and the method of the white oil B displacement treatment comprises the following steps: providing a cooling tank containing the white oil B, at least partially placing a first cooling roller and a second cooling roller in the white oil B, and driving the molten mixture to be displaced and initially cooled in the white oil B through the first cooling roller and the second cooling roller after the molten mixture is extruded;
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 coiling.
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 C2The white oil A with high viscosity is favorable for ensuring the mixing effect of the polyethylene melt and the white oil on one hand; on the other hand, the viscosity of the white oil A is high, so that low-temperature extrusion can be realized in the extrusion process, the degradation of the ultra-high molecular weight polyethylene is effectively prevented, and the performance of the film is improved. Meanwhile, in the step of cooling and forming, a white oil B cooling device is provided before water cooling treatment, at least part of the first cooling roller and the second cooling roller are placed in the white oil B with lower viscosity, and the white oil A with higher viscosity in the ultra-high molecular weight polyethylene/white oil A mixture is replaced by being driven by the first cooling roller and the second cooling roller, so that the white oil component is favorably and fully eluted in the extraction process, and the performance of the obtained ultra-high molecular weight polyethylene battery diaphragm is ensured.
Drawings
Fig. 1 is a schematic structural diagram of a white oil B cooling device provided in an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to 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 relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically 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 ultrahigh molecular weight polyethylene, white oil A and white oil B, wherein the viscosity of the white oil A is 80-100 mm at the temperature of 40 DEG C2(ii) and the viscosity of the white oil B is less than the viscosity of the white oil a;
s02, after feeding the ultrahigh molecular weight polyethylene and the white oil A, 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;
s03, performing replacement-cooling treatment on the substrate by using a cooling roller; the displacement-cooling treatment comprises white oil B displacement treatment and water cooling treatment, and the method of the white oil B displacement treatment comprises the following steps: providing a cooling tank containing the white oil B, at least partially placing a first cooling roller and a second cooling roller in the white oil B, and driving the molten mixture to be displaced and initially cooled in the white oil B through the first cooling roller and the second cooling roller after the molten mixture is extruded;
and S04, 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 coiling.
The embodiment of the invention provides a preparation method of an ultra-high molecular weight polyethylene battery diaphragmMethod, viscosity at 40 ℃ is 80-100 mm2The 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 viscosity of the white oil A is high, so that low-temperature extrusion can be realized in the extrusion process, the degradation of the ultra-high molecular weight polyethylene is effectively prevented, and the performance of the film is improved. Meanwhile, in the step of cooling and forming, a white oil B cooling device is provided before water cooling treatment, at least part of the first cooling roller and the second cooling roller are placed in the white oil B with lower viscosity, and the white oil A with higher viscosity in the ultra-high molecular weight polyethylene/white oil A mixture is replaced by being driven by the first cooling roller and the second cooling roller, so that the white oil component is favorably and fully eluted in the extraction process, and the performance of the obtained ultra-high molecular weight polyethylene battery diaphragm is ensured.
Specifically, in step S01, the ultra-high molecular weight polyethylene has the advantages of almost zero melt flowability and almost no deformation 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 to 250 ten thousand, the ultra-high molecular weight polyethylene in the range has high mechanical strength and good low temperature resistance, and the ultra-high molecular weight polyethylene used as a battery diaphragm has the advantages of long service life and good low temperature resistance. 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 former of the ultra-high molecular weight polyethylene in the wet-process diaphragm preparation process, is uniformly dispersed with the ultra-high molecular weight polyethylene before film forming, and is removed by extraction after the film forming, and pore channels are formed at positions of the finally obtained substrate where the white oil A is removed to form an electrolyte channel. Specifically, the viscosity of the white oil A is 80-100 mm at the temperature of 40 DEG C2And s. At the moment, the temperature of the white oil A is higher, so that the mixing effect of the polyethylene melt and the white oil is favorably ensured; meanwhile, the extrusion temperature in the extrusion process can be effectively reduced, so that the degradation of the ultra-high molecular weight polyethylene can be effectively prevented, and the thin film property can be improvedCan be used.
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 with white oil B with lower viscosity. Furthermore, in the subsequent extraction process, the white oil B has low viscosity, so that the white oil B is beneficial to being fully removed, a better pore structure is formed, and the passing of electrolyte is facilitated; while preventing the 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 for treatment. In some embodiments, the ultra-high molecular weight polyethylene and the white oil A may be mixed and then fed into the extruder. In other embodiments, the ultra-high molecular weight polyethylene and the white oil A are separately fed from different feeding ports of the extruder and then subjected to melt extrusion.
In a preferred embodiment, the weight percentage of the ultra-high molecular weight polyethylene is 15-20% based on 100% of the total weight of the ultra-high molecular weight polyethylene and the white oil A, so that a substrate which is uniform and flat and has good film performance can be obtained. If the content of the ultra-high molecular weight polyethylene is too low, the molten mixture is excessively olefinic, and the film-forming property 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, non-melted ultra-high molecular weight polyethylene particles are easy to appear in the obtained membrane layer, and the ultra-high molecular weight polyethylene particles are broken in the subsequent stretching process, so that the qualified diaphragm cannot be prepared.
In the embodiment of the invention, the viscosity of the white oil A is 80-100 mm2Therefore, at a lower extrusion temperature, the viscosity of the ultra-high molecular weight polyethylene and the viscosity of the white oil are relatively close to each other, and a molten and uniform mixture is obtained. In a specific embodiment, the temperature of the extrusion treatment of the extruder is 160-190 ℃, so that a good extrusion effect is obtained. 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 influenced; if the temperature of the extrusion process is too low,it is not favorable for sufficient melt extrusion.
Furthermore, in the extrusion process of the extruder, the rotating speed of the screw is 100-300 rpm, which is beneficial to obtaining eutectic with good shearing effect. If the rotating speed of the screw is too high, the polymer is degraded due to too large shearing heat of the polymer, and the performance of the finally obtained battery diaphragm is further influenced.
In the above step S03, the substrate is subjected to the replacement-cooling process sheet. The embodiment of the invention is different from the conventional cooling treatment method in that the replacement-cooling treatment is adopted, and the replacement-cooling treatment comprises a white oil B replacement treatment step and a water cooling treatment step. Specifically, a white oil B replacement treatment step is carried out, and the white oil A with high viscosity in the substrate obtained after extrusion is replaced by the white oil B with low viscosity; further, water cooling treatment is carried out on the white oil B through displacement treatment, and finally the substrate is obtained.
In the embodiment of the invention, the viscosity of the white oil B is less than that of the white oil A, so that the white oil B can be removed by extraction after being replaced with the white oil A in the film layer to form a pore structure. Preferably, the viscosity of the white oil B is 40-50 mm at the temperature of 40 DEG C2(s) and the viscosity difference between the white oil B and the white oil A is less than 50mm2And s. In this case, the white oil B has a suitable viscosity and can be removed by an extractant, in particular dichloromethane, trichloromethane, carbon tetrachloride; and the viscosity difference verified facilitates the displacement between white oil a and white oil B.
In a specific embodiment, the white oil B displacement treatment method is as follows: providing a cooling tank containing the white oil B, and at least partially placing a first cooling roller and a second cooling roller in the white oil B to form a white oil B cooling device in a combination manner, as shown in figure 1. After the molten mixture is extruded, the molten mixture is driven by the first cooling roller and the second cooling roller to carry out primary cooling and white oil replacement in the white oil B.
Further, in the step of white oil B replacement treatment, heat conduction 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 conduction oil of the first cooling roller and the temperature of the heat conduction oil of the second cooling roller are the same as the temperature of the white oil B. This temperature facilitates the initial shaping of the molten mixture and the efficient displacement during the shaping.
The primarily formed substrate after the white oil B replacement treatment is further subjected to water cooling treatment, preferably, the water cooling treatment method comprises the following steps: and (3) introducing cooling water into the third cooling roller, and cooling and forming the substrate formed by the white oil B replacement treatment by the third cooling roller.
In the embodiment of the present invention, preferably, a scraper for scraping off white oil on the surface of the primary substrate is disposed between the second cooling roller and the third cooling roller, so as to ensure that the oil content on the surface of the obtained base body is relatively uniform, and further, the base body is uniformly heated in the subsequent stretching process (where there are many places, the heating effect is good, and the difference between the heating effect and the stretching effect of other places is obvious), so as to achieve uniform stretching.
In 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 realized by a conventional method. Preferably, the extractant used for the extraction is at least one selected from dichloromethane, trichloromethane and tetrachloromethane, which is favorable for the sufficient elution of the white oil B, and dichloromethane is particularly preferred.
The following description will be given with reference to specific examples.
Example 1
A preparation method of an 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 85mm2White oil A and a viscosity of 50mm2A white oil B per second;
s12, mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
s13, performing replacement-cooling treatment on the molten mixture from the die head through a cooling roller; the displacement-cooling treatment comprises white oil B displacement treatment and water cooling treatment, and the method of the white oil B displacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing at least part of a first cooling roller and a second cooling roller in the white oil B at the temperature of 80 ℃, introducing heat conduction oil into the first cooling roller and the second cooling roller, setting the temperature to be 80 ℃, extruding the molten mixture, driving the extruded molten mixture by the first cooling roller and the second cooling roller, and performing replacement and primary cooling in the white oil B; the water cooling treatment method comprises the following steps: cooling water is introduced into 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 on the cooled substrate, and then carrying out heat setting and coiling, wherein the linear speed during extraction is 35m/min, an extractant dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 400 kg/h.
Example 2
A preparation method of an 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 85mm2White oil A and a viscosity of 50mm2A white oil B per second;
s22, mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 195 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
s23, performing replacement-cooling treatment on the substrate from the die head through a cooling roller; the displacement-cooling treatment comprises white oil B displacement treatment and water cooling treatment, and the method of the white oil B displacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing at least part of a first cooling roller and a second cooling roller in the white oil B at the temperature of 80 ℃, introducing heat conduction oil into the first cooling roller and the second cooling roller, setting the temperature to be 80 ℃, extruding the molten mixture, driving the extruded molten mixture by the first cooling roller and the second cooling roller, and performing replacement and primary cooling in the white oil B; the water cooling treatment method comprises the following steps: cooling water is introduced into the third cooling roller, and the temperature is set to be 15 ℃;
s24, sequentially carrying out longitudinal stretching, primary transverse stretching, extraction and secondary transverse stretching on the cooled substrate, and then carrying out heat setting and coiling, wherein the linear speed during extraction is 35m/min, an extractant dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 400 kg/h.
Example 3
A preparation method of an 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 85mm2White oil A and a viscosity of 50mm2A white oil B per second;
s32, mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/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 ultrahigh molecular weight polyethylene and the white oil A;
s33, performing replacement-cooling treatment on the substrate from the die head through a cooling roller; the displacement-cooling treatment comprises white oil B displacement treatment and water cooling treatment, and the method of the white oil B displacement treatment comprises the following steps: providing a cooling tank containing the white oil B, placing at least part of a first cooling roller and a second cooling roller in the white oil B at the temperature of 80 ℃, introducing heat conduction oil into the first cooling roller and the second cooling roller, setting the temperature to be 80 ℃, extruding the molten mixture, driving the extruded molten mixture by the first cooling roller and the second cooling roller, and performing replacement and primary cooling in the white oil B; the water cooling treatment method comprises the following steps: cooling water is introduced into the third cooling roller, and the temperature is set to be 15 ℃;
and S34, 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 coiling, wherein the linear speed during extraction is 35m/min, an extractant dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 400 kg/h.
Comparative example 1
A preparation method of an 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 85mm2S white oil A;
D12. mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
D13. cooling the substrate from the die head by a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting sheet roller and a second casting sheet roller which are internally communicated with heat conduction oil, the heat conduction oil is communicated in the rollers, the temperature is set to be 80 ℃, cooling water is communicated in a third casting sheet roller, and the temperature is set to be 15 ℃;
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 coiling, wherein the linear speed during extraction is 35m/min, an extraction agent dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 400 kg/h.
Comparative example 2
A preparation method of an 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 85mm2S white oil A;
D22. mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
D23. cooling the substrate from the die head by a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting sheet roller and a second casting sheet roller which are internally communicated with heat conduction oil, the heat conduction oil is communicated in the rollers, the temperature is set to be 80 ℃, cooling water is communicated in a third casting sheet roller, and the temperature is set to be 15 ℃;
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 coiling, wherein the linear speed during extraction is 35m/min, an extractant dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 1800 kg/h.
Comparative example 3
A preparation method of an 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 85mm2S white oil A;
D32. mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
D33. cooling the substrate from the die head by a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting sheet roller and a second casting sheet roller which are internally communicated with heat conduction oil, the heat conduction oil is communicated in the rollers, the temperature is set to be 80 ℃, cooling water is communicated in a third casting sheet roller, and the temperature is set to be 15 ℃.
Experiments show that the membrane surface wrinkling phenomenon is severe because the viscosity of the white oil B is low, resulting in high melt viscosity.
Comparative example 4
A preparation method of an 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 85mm2S white oil A;
D42. mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/h), and carrying out melt extrusion treatment under the conditions that the temperature is 185 ℃ and the rotating speed of an extrusion screw is 200rpm to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
D43. cooling the substrate from the die head by a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting sheet roller and a second casting sheet roller which are internally communicated with heat conduction oil, the heat conduction oil is communicated in the rollers, the temperature is set to be 80 ℃, cooling water is communicated in a third casting sheet roller, and the temperature is set to be 15 ℃;
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 coiling, wherein the linear speed during extraction is 35m/min, an extraction agent dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 1200 kg/h.
Comparative example 5
A preparation method of an 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 85mm2S white oil A;
D52. mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/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 ultrahigh molecular weight polyethylene and the white oil A;
D53. cooling the substrate from the die head by a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting sheet roller and a second casting sheet roller which are internally communicated with heat conduction oil, the heat conduction oil is communicated in the rollers, the temperature is set to be 80 ℃, cooling water is communicated in a third casting sheet roller, and the temperature is set to be 15 ℃;
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 coiling, wherein the linear speed during extraction is 35m/min, an extraction agent dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 1200 kg/h.
Comparative example 6
A preparation method of an 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 85mm2S white oil A;
D62. mixing the ultrahigh molecular weight polyethylene and the white oil A according to a weight ratio of 1: 5, uniformly mixing, feeding into an extruder (the total feeding amount is 300kg/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 ultrahigh molecular weight polyethylene and the white oil A;
D63. cooling the substrate from the die head by a cooling roller; wherein the cooling process comprises: the substrate coming out of the die head passes through a first casting sheet roller and a second casting sheet roller which are internally communicated with heat conduction oil, the heat conduction oil is communicated in the rollers, the temperature is set to be 80 ℃, cooling water is communicated in a third casting sheet roller, and the temperature is set to be 15 ℃;
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 coiling, wherein the linear speed during extraction is 35m/min, an extractant dichloromethane is injected into a groove, and the supplement amount of fresh dichloromethane is 1800 kg/h.
The ultra-high molecular weight polyethylene battery separators provided in examples 1 to 3 and comparative examples 1 to 6 were subjected to an extraction efficiency test in the following manner:
(1) taking a membrane sample of 10cm × 10cm at the inlet of the extraction tank, and weighing m 0;
(2) removing the membrane sample from the outlet of the extraction tank to 10cm × 10cm, and weighing m 1;
(3) soaking the sample in clean dichloromethane for 3 minutes, then airing, and weighing m 2;
(4) soaking the sample in clean dichloromethane for 3 minutes, then airing, and weighing m 3;
repeating the above steps until the mass is unchanged, and recording as mz
The extraction efficiency is (m0-m1)/(m0-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 concluded that the higher the extrusion temperature, the lower the mechanical strength of the finished product; however, if the extrusion temperature is too low, poor melting may result. It can be seen from comparative examples 1, 2 and 4 that the higher the viscosity of the white oil used for extrusion, the greater the amount of methylene chloride recycled.
At present, the processing method of the ultra-high molecular weight polyethylene diaphragm mostly adopts the process of the comparative example 5, 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 has high strength, and the degradation of polyethylene can be effectively slowed down due to lower processing temperature; 2, the process has low energy consumption, 0.3-0.5 kg of steam is needed for separating 1kg of mixed solution of dichloromethane and white oil, and the amount of circulating dichloromethane in the embodiment of the invention is about one third of that in the general process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of an ultra-high molecular weight polyethylene battery diaphragm is characterized by comprising the following steps:
providing ultrahigh molecular weight polyethylene, white oil A and white oil B, wherein the viscosity of the white oil A is 80-100 mm at the temperature of 40 DEG C2(ii) 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 the heating condition to obtain a substrate formed by co-melting the ultrahigh molecular weight polyethylene and the white oil A;
performing replacement-cooling treatment on the substrate by using a cooling roller; the displacement-cooling treatment comprises white oil B displacement treatment and water cooling treatment, and the method of the white oil B displacement treatment comprises the following steps: providing a cooling tank containing the white oil B, at least partially placing a first cooling roller and a second cooling roller in the white oil B, and driving the molten mixture to be displaced and initially cooled in the white oil B through the first cooling roller and the second cooling roller after the molten mixture is extruded;
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 coiling.
2. The method for preparing the ultra-high molecular weight polyethylene battery separator as claimed in claim 1, wherein the viscosity of the white oil B is 40-50 mm at a temperature of 40 ℃2(s) and the viscosity difference between the white oil B and the white oil A is less than 50mm2/s。
3. The method of preparing an ultra-high molecular weight polyethylene battery separator according to claim 1, wherein the temperature of the extrusion treatment is 160 to 190 ℃.
4. The method for preparing the ultra-high molecular weight polyethylene battery separator according to claim 3, wherein the screw rotation speed is 100-300 rpm in the extrusion process.
5. The method of preparing an ultra-high molecular weight polyethylene battery separator according to any one of claims 1 to 4, wherein 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.
6. The method of preparing an ultra-high molecular weight polyethylene battery separator according to claim 5, wherein the ultra-high molecular weight polyethylene has a weight average molecular weight of 150 to 250 ten thousand.
7. The method for preparing the ultra-high molecular weight polyethylene battery separator according to any one of claims 1 to 4, wherein in the step of performing the white oil B replacement treatment, heat conduction 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 conduction oil of the first cooling roller and the second cooling roller is the same as the temperature of the white oil B.
8. The method for preparing an ultra-high molecular weight polyethylene battery separator according to any one of claims 1 to 4, wherein the water cooling treatment method comprises: and (3) introducing cooling water into the third cooling roller, and cooling and forming the substrate formed by the white oil B replacement treatment by the third cooling roller.
9. The method of claim 8, wherein a doctor blade for scraping off white oil on the surface of the preform substrate is disposed between the second cooling roller and the third cooling roller.
10. The method for preparing an ultra-high molecular weight polyethylene battery separator as claimed in any one of claims 1 to 4, wherein the extraction agent used for the extraction is at least one selected from dichloromethane, trichloromethane and tetrachloromethane.
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