CN112201900A - Film with uniform water absorption and preparation method thereof - Google Patents
Film with uniform water absorption and preparation method thereof Download PDFInfo
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- CN112201900A CN112201900A CN202011087573.4A CN202011087573A CN112201900A CN 112201900 A CN112201900 A CN 112201900A CN 202011087573 A CN202011087573 A CN 202011087573A CN 112201900 A CN112201900 A CN 112201900A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
A film with uniform water absorption and a preparation method thereof are disclosed, which comprises the steps of mixing and heating polyethylene, paraffin oil, silicon dioxide nano particles and 4, 4' -thiobis (6-tert-butyl-m-cresol) in batches, extruding and forming, respectively stretching transversely and longitudinally, and then stretching in two dimensions according to the light transmittance distribution of the film. And after stretching is finished, spraying water, determining a region to be stretched according to a water layer distribution diagram, performing two-dimensional stretching, and drying to form a film, thereby obtaining the lithium battery diaphragm with uniform water absorption characteristics.
Description
Technical Field
The invention relates to the technical field of lithium battery diaphragms and preparation thereof.
Background
The diaphragm is an important component in the lithium battery, and directly determines the service performance and safety of the lithium battery. Typically the separator is an insulating material having a porous structure. In the case of a separator, it is generally necessary to ensure a certain porosity and pore size so that ions can smoothly migrate. Too high results in a decrease in the strength of the separator, and too low results in an increase in the internal resistance. The uniformity of the film also affects the electrolyte wetting of the film, thereby affecting the internal resistance of the cell. Moreover, in abnormal situations, an excessive current will cause the temperature to rise to T1, closing the membrane opening, stopping ion migration and avoiding further danger. But if the temperature is raised too high to T2, it also causes the membrane to rupture, thereby damaging the cell. Only by appropriately lowering the temperature T1, the temperature T2 can be raised to make the battery safer to use. Therefore, for the lithium battery diaphragm, the parameters affect the safety and performance of the subsequent battery during use.
At present, the above problems are solved by adopting a more complex process mode in the industry, for example, a PE diaphragm is bombarded by gamma rays and reacts with polar methoxy polyethylene oxide acrylate to form a film; or mixing Al2O3And the nano ceramic particles are uniformly coated on the surface of the PE diaphragm to form a film and the like. Although the existing various modes solve the problems to a certain extent, the effect is limited, the cost is high, a new process needs to be introduced, and the process maturity is yet to be improved.
The industry mostly performs one-by-one optimization of single parameters to achieve security and improve performance. The membrane thickness is detected, for example, with an optical device. However, this is time consuming and laborious and the multi-parameter crossover is difficult to control. Meanwhile, the consistency of comprehensive performance of all parameters is not realized, and the significance on the safety and the performance improvement of the battery is achieved.
Particularly, the non-uniformity of the opening size and the porosity of the separator greatly affects the safety of the battery, and the thin film breakdown phenomenon easily occurs at a position having a large opening and a large porosity, while the electrical properties are affected at a position having a small opening and a small porosity. In the prior art, firstly, detection can be performed only aiming at the single parameter, and cannot be comprehensively considered; secondly, detection is only carried out after the final preparation is finished, and the front-stage process cannot be fed back and controlled even if a problem is found, so that the method belongs to quality inspection type detection and is not part of a production process; and thirdly, even for a single parameter, the prior art only detects the porosity size and the opening size, but does not propose the detection of the pore distribution uniformity and the opening size uniformity.
However, if a method capable of comprehensively representing each parameter is selected for process control, the control precision requirement of the process is high, and how to realize the process control of the composite parameter by using a simple method is not mentioned in the prior art.
Therefore, a method for preparing a lithium battery diaphragm by fully utilizing the existing process method and efficiently realizing better safety and better electrical property of the battery on the basis of optimizing the preparation process is urgently needed.
Disclosure of Invention
In view of the above problems, the present invention has been made to provide a lithium battery separator and a method for preparing the same, which overcome or at least partially solve the above problems.
A method for preparing a film with uniform water absorption,
the raw material A is polyethylene and comprises the following two parts
A1: molecular weight 6.5X 106-8.5×106The polyethylene particles of (a);
a2: the density is 0.966-0.983g/cm3The polyethylene particles of (a);
the raw material B is paraffin oil; the raw material C is silicon dioxide nano particles with the diameter of 20-30 nm; the raw material D is 4, 4' -thiobis (6-tert-butyl-m-cresol);
step 1: the 4 raw materials are heated and mixed in batches: a first batch of material A1 and material D and half the weight of material B; adding the raw material A2 and the other half weight of the raw material B in a second batch; adding raw material C for the third batch;
step 2: injecting the mixed slurry into an extruder to extrude into a thick film;
and step 3: sequentially carrying out longitudinal stretching and transverse stretching on the thick film at a stretching ratio of 6-7 to obtain a thin film, and extracting after the stretching is finished;
and 4, step 4: the film is conveyed to a two-dimensional stretching device, light transmittance abnormal points on the film are obtained, and a stretching area is determined according to the distribution of the abnormal points;
and 5: correspondingly controlling a two-dimensional stretching device to perform a film two-dimensional stretching process according to the determined stretching area;
step 6: moving the water spraying device to the position above the film for quantitative water spraying, forming a water layer on the surface of the film after the water spraying is finished, moving the water spraying device away, starting a light source and a camera for detection, and obtaining film images of the completion time of the water spraying and the standing time of 10 minutes, 30 minutes and 60 minutes, so as to determine an abnormal water absorption area of the film;
and 7: the film production and manufacturing process can be controlled in a feedback mode according to the distribution of the water absorption abnormal areas, and the method specifically comprises the following steps:
(1) if the abnormal water absorption areas are distributed irregularly in a large area, the production process has a large defect, and the production line should be stopped for maintenance;
(2) if the water absorption abnormal areas are distributed in the longitudinal direction, controlling a longitudinal stretching device of the two-dimensional stretching mechanism to longitudinally stretch the corresponding positions, and not stretching the rest positions; or stretching the rest positions without longitudinally stretching the corresponding positions;
(3) if the water absorption abnormal area is distributed in the transverse direction, controlling a transverse stretching device of the two-dimensional stretching mechanism to transversely stretch the corresponding position, and not stretching the rest positions; or stretching the rest positions without stretching the corresponding positions in the transverse direction;
and 8: and drying for 30 minutes, and coiling after drying.
The distance between the water spraying device and the film is less than 10 cm.
The grain diameter of the sprayed water drops is ensured to be 0.05-0.15 mm.
Also comprises an oil content detection step.
A film having uniform water absorption, which is prepared using the above method.
Invention and technical effects
1. The uniformity of the water absorption characteristic of the film is utilized to comprehensively measure the uniformity of the porosity and the uniformity of the size of the open pore, so that the complex parameters can be comprehensively considered, and the method is suitable for the control of a production line. And the preparation process is controlled by the test result feedback of the uniformity of the water absorption characteristic, so that the film with higher safety and better electrical property can be produced.
2. The preparation materials, the flow steps and the process parameters are optimized, the raw material for preparing the lithium battery diaphragm and the corresponding preparation method are provided, the opening can be closed when the temperature of the battery is abnormally increased, the mechanical strength of the film is high, the high temperature resistance and the low internal resistance are realized, the high-performance lithium battery diaphragm is prepared, the lithium battery diaphragm can be protected in time when the temperature of the battery is abnormal, and the lithium battery diaphragm is high in temperature resistance, low in resistance, high in safety and excellent in electrical performance.
3. The consistency of all parameters of the battery diaphragm is provided for the first time, so that the influence on the safety and the battery performance is large. The method comprehensively optimizes a plurality of parameters, utilizes the light transmittance capable of comprehensively representing a plurality of conventional diaphragm parameters as a consistency standard, and utilizes the light transmittance to control the manufacture of the diaphragm, thereby efficiently realizing the high-safety and high-performance diaphragm and being particularly suitable for large-batch actual production processes.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a flow chart of a process for making a separator
FIG. 2 is a process flow diagram of a membrane water absorption test
FIG. 3 is a top view of a two-dimensional stretching process of a separator
FIG. 4 is a rear view of a two-dimensional stretching process of a separator
FIG. 5 is a front view of a process for stretching a separator in two dimensions
Fig. 6 is a schematic diagram of a two-dimensional tensile and water absorption test process of the separator.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
Diaphragm preparation method
The feedstock a is polyethylene, and in particular, may comprise the following two fractions, and the preferred weight ratio of the two is 1:1.53, according to a number of experiments.
A1: molecular weight 6.5X 106-8.5×106The polyethylene particles of (a);
a2: the density is 0.966-0.983g/cm3The polyethylene particles of (a);
the raw material B is paraffin oil; the raw material C is silicon dioxide nano particles with the diameter of 20-30 nm; the raw material D is 4, 4' -thiobis (6-tert-butyl-m-cresol);
wherein the weight ratio of the raw material A to the raw material B is 27: 43, the weight ratio of the raw material C to the raw material A is 1.3: 100, the weight ratio of the raw material D to the raw material A is 0.7: 100.
step 1: mixing the raw material A1, the raw material D and half of the raw material B by weight, heating to 70-110 ℃, stirring for 25 minutes, and keeping the stirring speed at 340 r/min.
Step 2: adding the raw material A2 and the other half of the raw material B by weight into the stirred material in the step 1, mixing, heating to 90-130 ℃, stirring for 5 minutes, and keeping the stirring speed at 340 r/min.
And step 3: adding the raw material C into the stirred material in the step 2, keeping the temperature at 140 ℃ and 170 ℃, stirring for 30 minutes, increasing the stirring speed to 520 r/min, and finally obtaining the slurry.
And 4, step 4: and injecting the mixed slurry into an extruder for extrusion, and keeping the temperature of the extruder at 170-230 ℃ and the extrusion rate at 1100 g/min.
And 5: cooling and solidifying the extrudate on a cooling roller to form a thick film with the thickness of 400-2500 mu m, wherein the cooling temperature is 20-70 ℃, and solid-liquid phase separation or liquid-liquid phase separation occurs in the cooling and solidifying process, so that a microporous structure is formed in the extrudate.
Step 6: setting the temperature of a preheating roller, a longitudinal stretching roller and a cooling roller to be 90 ℃, 120 ℃ and 20 ℃, and longitudinally stretching the thick film through the preheating roller, the longitudinal stretching roller and the cooling roller in sequence to obtain a semi-thick film with the extension ratio of 6-7;
and 7: setting the temperature of a preheating roller, the temperature of a transverse stretching roller and the temperature of a cooling roller to be 100 ℃, 125 ℃ and 90 ℃, and carrying out transverse stretching on the semi-thick film through the preheating roller, the transverse stretching roller and the cooling roller in sequence to obtain a film with the elongation ratio of 6-7;
and 8: and (3) conveying the film into a dichloromethane extraction box for extraction, wherein the temperature in the extraction box is 20-35 ℃, and the extraction time is 4 hours. Drying after extraction;
and step 9: the film is conveyed to a two-dimensional stretching device for fine tuning stretching in both transverse and longitudinal directions, and the stretching temperature is kept at 130-150 ℃. Meanwhile, the light transmittance distribution of the film is monitored in the stretching process, so that the force of the stretching device at different stretching positions is controlled, the light transmittance consistency of the film at different positions is adjusted, and the film with better consistency is finally obtained.
Step 10: and cooling to form the film after the two-dimensional stretching is finished.
Step 11: and (5) testing parameters such as thickness, cleanliness, strength, wettability, air permeability and the like by using detection equipment.
The diaphragm prepared according to the raw material proportion and the process can timely close the open pore when the temperature of the battery is abnormally increased, and can be kept at a higher temperature without the problem of membrane rupture. Meanwhile, the internal resistance is low, and the stability is good.
Wherein thick film is understood in the art to mean a thicker film formed from the paste extruded in the extruder; the semi-thick film is a film with reduced thickness after being stretched in one direction; the film is a film with the thickness close to that of a final finished product after the two-direction stretching process.
In step 3, the mixture may be directly heated to the desired temperature as described above. In particular, however, the heating in step 3 may be performed by alternating heating-holding-heating to give sufficient contact reaction time for each material to obtain better film properties. Specifically, the heating in step 3 may be performed according to the following formula:
T= a*(sin(t)+b*t2)+X
where T is the heating temperature, T is the time, a, b are empirical coefficients, preferably a =5, b =0.1, and X is the temperature in step 2, typically 90-130 ℃. Where T is in units of deg.C, T is in units of minutes and X is in units of deg.C.
In this case, it is necessary to maintain the temperature and stir the mixture after the heating temperature T reaches the temperature required in step 3.
Two-dimensional stretching process in diaphragm manufacturing
In the stretching process, only the thickness of the film is generally monitored to ensure thickness consistency and thus improve the performance of the film. In practice, a number of parameters of the film affect its performance. For example: porosity, pore size, film density, breathability, etc. These properties are usually measured only after the film has been produced, using a number of different devices, to determine whether the film is acceptable. First, doing so requires more equipment; secondly, the detection is post detection, and the produced inferior products cannot be avoided.
The invention provides the detection of the film parameters in the film stretching process and controls the stretching action at the same time, thereby ensuring that the film with higher quality is stretched. However, if a plurality of devices are used for parameter detection, the devices are abnormally complicated, and it is difficult for the control algorithm to balance a plurality of parameters. However, it has been found that, over many years, the above-mentioned non-uniformities in various parameters are ultimately reflected in non-uniformities in the light transmission of the film. Therefore, in order to rapidly control the stretching device in production practice, the invention proposes to use the light transmittance to perform the control of the film stretching, thereby comprehensively controlling the above parameters and obtaining a higher quality diaphragm. Therefore, this is also one of the points of the present invention, and the process thereof will be set forth in detail below.
The two-dimensional stretching equipment comprises a left moving roller 1, a right moving roller 2, an upper left clamping roller 3-1, a lower left clamping roller 3-2, an upper right clamping roller 4-1, a lower right clamping roller 4-2, a rear side edge clamping part 5-1, a rear side edge lower clamping part 5-2, a front side edge clamping part 6-1, a front side edge lower clamping part 6-2, a rear side edge driving part 5-3, a front side edge driving part 6-3, a camera 7 and a surface light source 8.
The left moving roller 1 and the right moving roller 2 are respectively positioned at two ends of the device and used for transmitting the film M, and are simultaneously used for generating left or right pulling force on the film M positioned on the left moving roller and the right moving roller when the film M is respectively translated leftwards or rightwards, and when the other end of the film M is relatively fixed, the longitudinal stretching of the diaphragm is realized.
The upper left clamping roller 3-1 and the lower left clamping roller 3-2 are arranged oppositely up and down and used for clamping the left side of the film M. Wherein the left lower clamping roller 3-2 is fixedly arranged, and the left upper clamping roller 3-1 can move up and down. The upper left pinch roller 3-1 moves downward when the pinching is required, thereby forming the pinching of the left side edge of the film M with the lower left pinch roller 3-2. The upper left clamping roller 3-1 is a plurality of short rollers which can move up and down independently, and the up-and-down movement distance is accurate and controllable. The lower left pinch roll 3-2 is a long roll.
The upper right clamping roller 4-1 and the lower right clamping roller 4-2 are arranged oppositely up and down and used for clamping the right side of the film M. Wherein the right lower clamping roller 4-2 is fixedly arranged, and the right upper clamping roller 4-1 can move up and down. The upper right pinch roller 4-1 moves downward when the pinching is required, thereby forming the pinching of the right side edge of the film M with the lower right pinch roller 4-2. The upper right pinch roll 4-1 is a single long roll, the distance of which up and down moves is precisely controllable. The lower right pinch roll 4-2 is a long roll.
When the upper left pinch roller 3-1 at different positions moves downward by different distances, different intervals are formed at different positions from the lower left pinch roller 3-2, thereby generating different pinching forces to the film M at the corresponding positions. At this time, if the right moving roller 2 moves rightwards, the film M is driven to move rightwards, and at this time, the clamping forces at different positions on the left side of the film M are different, so that for the driving force fixed by the right moving roller 2, the stretching degrees of the longitudinal strip regions of the film M at different positions in the transverse direction are different, and thus different stretching ratios can be generated for the longitudinal strip regions at different positions. Therefore, by controlling the different pitches formed by the upper left pinch roller 3-1 and the lower left pinch roller 3-2 at different positions, the draw ratio of the corresponding sliver region can be controlled. For more precise control, a denser, greater number of upper left pinch rollers may be provided, typically 10, but for higher control resolution, 20-30 may be provided.
When the upper right pinch roller 4-1 moves downwards to form a pinch on the right side edge of the film M together with the lower right pinch roller 4-2, if the left moving roller 1 moves leftwards, the film M is driven to move leftwards, and the film M is uniformly and longitudinally stretched.
Each back side edge clamping part 5-1 and each back side edge lower clamping part 5-2 are arranged oppositely up and down to form a back side edge clamping part together. A plurality of which are arranged along the rear side of the film M for clamping the rear side of the film M. The front side edge clamping part 6-1 and the front side edge lower clamping part 6-2 are arranged oppositely up and down and are a section of a whole, and the front side edge clamping part and the front side edge lower clamping part jointly form a front side edge clamping part used for clamping the front side edge of the film M. The main bodies of the rear side edge clamping part 5-1, the rear side edge lower clamping part 5-2, the front side edge clamping part 6-1 and the front side edge lower clamping part 6-2 are all made of rubber, and the film is prevented from being damaged during clamping. Meanwhile, the rubber is doped with fine iron particles during molding, thereby enhancing the strength of the rubber on the one hand and simultaneously being used for being attracted by the driving part.
The rear side driving part 5-3 is composed of electromagnets and is positioned at the rear side of the rear side edge clamping part 5-1 and the rear side edge lower clamping part 5-2, and the number of the rear side driving parts 5-3 is also a plurality and respectively corresponds to the rear side edge clamping parts which are arranged. The transverse strip-shaped area is used for attracting the corresponding rear side clamping part after being electrified, so that the transverse strip-shaped area corresponding to the position of the film clamped by the rear side clamping part is stretched. Therefore, by controlling the current magnitude of the different rear side driving portions 5-3, the backward stretching force of the rear side clamping portions corresponding to different positions can be controlled, thereby controlling the stretching ratio of the transverse strip-shaped area corresponding to the film. Of course, the front side holding part should fixedly hold the front side of the film while controlling the rear side driving part 5-3 to stretch.
The front side driving portion 6-3 is composed of electromagnets and is located on the front side of the front side clamping portion 6-1 and the front side of the front side lower clamping portion 6-2, and a plurality of rear side driving portions 6-3 are evenly distributed on the front side of the front side clamping portion and used for attracting the corresponding front side clamping portion after being electrified, so that the film clamped by the front side clamping portion is stretched. Although the front side upper holding part 6-1 and the front side lower holding part 6-2 are both single, the main body thereof is made of rubber, and has a certain flexibility. Therefore, by controlling the current of a certain front side driving portion 6-3, the relatively largest pulling force can be generated at the position of the front side clamping portion directly opposite to the front side driving portion 6-3, and the next largest pulling force can be generated at the position adjacent to the position of the front side clamping portion directly opposite to the front side driving portion 6-3. That is, even if only one of the front side driving portions 6-3 is energized, the entire front side of the film can be stretched, but the position corresponding to the front side driving portion 6-3 is stretched most, and the other positions are successively decreased in accordance with the stretch ratio at a distance therefrom. However, since the entire front-side holding portion is an integral whole along the front side of the film, the variation in the stretch ratio at such different positions is actually very small. Therefore, it is very suitable for the case where the stretching ratio at a certain position needs to be finely adjusted. Therefore, the method does not cause drastic change of consistency with an adjacent area due to control of micro stretching of a certain area, thereby ensuring accuracy and high efficiency of process control, and is also one of the invention points. Of course, in the two-dimensional stretching apparatus, only a fine stretching operation is performed, defects at individual positions are adjusted, and a large stretching ratio operation is not performed.
A surface light source 8 is provided above the film, and a plurality of surface light sources 8 may be provided since the film may be large. However, if the multi-surface light source combination is carried out, the light intensity of any position of the film is the same. The surface light source 8 is used to provide uniform illumination to the film.
The camera 7 is arranged below the film, and the film can be large and the field of view of the camera is limited, so that a plurality of cameras 7 can be arranged to splice the field of view. The camera 7 is for emitting light transmitted through the film from the light source 8 on the receiving surface, and taking an image of the film.
The obtained image is sent to a processor to carry out the following operations:
(1) each pixel point in the image is positionally mapped to an actual point on the film.
(2) Obtaining the gray value P of each pixel point in the imagei。
(3) Determining the mean gray-scale value P of the image0。
(4) If Pi-P0|/ P0>Q, then P isiThe corresponding film position point is marked as an abnormal point, wherein Q is a set threshold range, and can be selected according to the level of the requirement on the film consistency, and in order to take account of speed and precision, the Q value can be initially set to be small, for example, 0.01, so that a large number of abnormal points appear, but in this case, the inconsistency of many abnormal points is not unacceptable in practice. Further accurate screening is therefore required.
(5) Abandoning the isolated abnormal points, selecting the area with concentrated abnormal points, controlling the area light source 8 corresponding to the area to weaken the light intensity to 30% of the standard light intensity, recalculating the gray value of each pixel and the average gray value, and re-marking the abnormal points according to the relationship between the gray value and the average gray value. Thus, areas where the transmission is below normal will decay more rapidly and more severely, and will therefore be marked significantly. And controlling the area light source 8 corresponding to the area to improve the light intensity to 250% of the standard light intensity again, recalculating the gray value and the average gray value of each pixel, and re-marking the abnormal points according to the relationship between the gray value and the average gray value. Thus, areas with higher than normal transmission will have a faster and more severe gray scale value rise and will therefore also be marked clearly. Thus, the outlier can be redetermined. Through this kind of mode, can accurate screening anomaly to can avoid excessive and unnecessary tensile operation, practice thrift the production time, improve the film forming ability.
(6) And determining the distribution area of the newly determined abnormal points, and selecting a rectangular frame with the smallest area to cover the abnormal points, wherein the rectangular frame is used as an area to be stretched in two dimensions and is called a stretching area. Individual outliers that are isolated can be discarded from consideration.
The control method for longitudinal stretching and transverse stretching comprises the following steps:
firstly, when the stretching areas are uniformly distributed at all positions of the film, the upper right clamping roller 4-1 and the lower right clamping roller 4-2 are controlled to approach to clamp the right side of the film, and the left moving roller 1 moves leftwards.
When the stretching areas are distributed in a longitudinal strip shape, controlling the upper left clamping roller 3-1 at the corresponding position to gradually approach the lower left clamping roller 3-2, and generating the maximum clamping force on the position of the film with the minimum distance; the left upper nip roll 3-1 in the remaining positions is also close to the left lower nip roll 3-2, but at a larger pitch, producing less or even no nip force for that position of the film. And controlling the right moving roller 2 to translate to the right, so that the area corresponding to the maximum clamping force is intensively longitudinally stretched, and the rest area is slightly stretched or even not longitudinally stretched.
Thirdly, when the stretching areas are distributed in a transverse strip shape,
if the abnormal condition in the area is serious, inputting large current to the rear side driving part 5-3 at the corresponding position so as to generate large pulling force; and the rear side driving part 5-3 at the other positions inputs small current, thereby generating small tension even without generating tension. Such that the respective regions are laterally stretched and the remaining regions are slightly or not laterally stretched. At this time, the front side edge holding portion holds the side edge of the film as a whole.
If there is only a slight abnormal condition in the area, the difference from the peripheral light transmission condition is small. A large current is inputted to the front side driving part 6-3 at the corresponding position, so that a large tensile force is generated and the region corresponding to the position is laterally stretched. However, since the front side edge holding portion 6-1 and the front side edge lower holding portion 6-2 are single, a transverse tension is generated in other positions in the longitudinal direction of the film. But because the main body of the front side clamping part is made of rubber, the front side clamping part has certain flexibility. Therefore, the transverse tension generated at other positions is not greatly different from the transverse tension generated at the abnormal position. Thereby it is avoided that a certain position is stretched in the transverse direction, resulting in excessive stretching. At this time, the rear side edge holding portion holds the side edge of the film as a whole.
Finally obtaining the film by the raw material proportion and the preparation processThe temperature T1 is 100 ℃, the temperature T2 is 220 ℃, and the safety of the battery can be effectively ensured. Meanwhile, the thickness error is not more than 0.01 percent because the thickness of the film is 23 mu m; the film has good consistency of parameters such as opening size, porosity, pore distribution, wettability and the like, and the surface resistance of the film is lower than 0.41 omega cm2When assembled into a lithium battery, the internal resistance is 20.4% lower than that of the conventional film.
Those skilled in the art will appreciate that the above stretching process is best suited for use in conjunction with the preparation of the films proposed by the present invention. This does not mean that the stretching process cannot be used for the manufacture of other films. The conventional lithium battery separator may be manufactured using the above-described stretching process.
Although the two-dimensional stretching device can conveniently and quickly ensure the consistency of the film, especially the consistency of the comprehensive performance of a plurality of parameters such as the opening size, the porosity, the thickness, the density, the air permeability and the like. However, in order to further improve the electrical properties of the thin film, it is necessary to more accurately ensure the uniformity of the wettability, especially the uniformity of the size of the openings and the porosity distribution. In the prior art, post inspection is carried out, and a sample is generally required to be cut off for experimental test, so that the method is completely not suitable for online control in a production line. The parameters can be comprehensively characterized by the uniformity of the water absorption characteristics. This makes it possible to control the parameters for feedback control of the production process, as follows:
above the stretching zone, a water spraying device 9 is arranged, which is horizontally movable above the stretching zone. When water is needed to be sprayed, the water spraying device moves to the position above the film which is subjected to two-dimensional stretching, water is sprayed, and when the water is needed to be detected, the water spraying device is moved away from the position above the film in a translation mode, so that the light rays are prevented from being shielded and detected.
And after the two-dimensional stretching is finished, moving the water spraying device to the position above the film, and ensuring that the water spraying device and the film are parallel. Meanwhile, in order to test the effect, the distance between the water spraying device and the film needs to be ensured to be less than 10cm, and the preferred distance is 1-2 cm. If the distance is too large, water mist can be dispersed, and a water layer which is easy to detect cannot be formed on the surface of the film; and the interval undersize, the water layer on the film can form the adhesion with water jet equipment, thereby influences the water layer appearance and influences and detects the precision. Therefore, it is also one of the points of the invention.
After the water spraying device moves in place, the quantitative water spraying is carried out, and the grain diameter of the sprayed water drops is ensured to be 0.05-0.15 mm. After the water spraying is finished, a water layer is formed on the surface of the film. At this point, the water jet is removed, the light source and camera (both located above the film, not shown) are activated for detection, and a film image P0 is taken at the completion of water jet. It will be understood that the image is theoretically a film image of the aqueous layer.
Standing for 10 minutes, 30 minutes and 60 minutes respectively, and starting the light source and the camera again for detection to obtain the film images Pn at the corresponding time respectively. It can be understood that the water layer on the film is continuously adsorbed by the gaps of the film, so that the water layer images on the film are different at different moments, and the speed and uniformity of adsorption comprehensively reflect the wettability, the opening size and the uniformity and consistency of the porosity of the film.
And comparing the images shot at different moments with the standard images in the database to obtain the water absorption condition of the film. Meanwhile, the distribution of the water layer on each image is analyzed independently, and the consistency of the water absorption condition of each position of the film can be obtained. Thereby obtaining the film water absorption abnormal area.
The film production and manufacturing process can be controlled in a feedback mode according to the detection result, and the method specifically comprises the following steps:
(1) if the abnormal water absorption areas are distributed irregularly in a large area, the production process has a large defect, and the production line should be stopped for maintenance.
(2) If the water absorption abnormal areas are distributed in the longitudinal direction, controlling a longitudinal stretching device of the two-dimensional stretching mechanism to longitudinally stretch the corresponding positions, and not stretching the rest positions; or the corresponding position is longitudinally not stretched, and the rest positions are stretched.
(3) If the water absorption abnormal area is distributed in the transverse direction, controlling a transverse stretching device of the two-dimensional stretching mechanism to transversely stretch the corresponding position, and not stretching the rest positions; or the corresponding position is not stretched in the transverse direction, and the rest positions are stretched.
(4) And after the water absorption test is finished, drying for 30 minutes, and coiling after the drying is finished.
Through the water absorption test and the process control, the temperature consistency of T2 at each position of the film in the lithium battery is improved by 10%, so that local breakdown is avoided. Meanwhile, the uniformity of the surface resistance is improved by 6 percent.
The paraffin oil is used in the preparation process of the film, and the paraffin oil is extracted by dichloromethane subsequently, but the paraffin oil is extracted cleanly, so that the performance parameters of the film are greatly influenced. If the grease is not extracted completely, the porosity and air permeability of the diaphragm are directly influenced, and the internal resistance, the cyclicity and the like of the battery are further influenced. In the prior art, chemical extraction is adopted to prolong the extraction time or extract for multiple times, but the time and the economic cost are increased. Therefore, the method is particularly important for measuring the oil content of the film.
In the prior art, a part of a sample is intercepted, and the oil content of the sample is tested by using a chemical reagent or an evaporation mode. However, this method is only suitable for the later test, and the sample cannot be intercepted on the production line, which may cause damage to the whole film. And the later-stage test result can only be used for judging whether the film is qualified or not, and the production process cannot be controlled on line in real time according to the result.
The invention provides an online oil content testing method applicable to a production line, which comprises the following steps:
the film conveying roller comprises a left roller and a right roller and is used for conveying the film M to the oil absorption stamping area; the oil absorption imprinting material is used for separating out oil in the film under the action of external force and forming oil stains on the surface of the material; the oil absorption imprinting material conveying roller is used for conveying the oil absorption imprinting material to the position above the thin film in the oil absorption imprinting area; the pressing rollers are arranged in the oil absorption pressing area and are arranged in an upper row and a lower row, each row is provided with a plurality of rollers which are positioned on the outer sides of the oil absorption pressing material and the thin film M, when the upper row and the lower row of pressing rollers rotate and extrude, the oil absorption pressing material is fully contacted with the thin film M, the grease in the thin film M is separated out, and the grease is printed on the oil absorption pressing material; the oil absorption imprinting material conveying roller also comprises a roller positioned on the upper side and used for vertically and upwards conveying the oil absorption imprinting material subjected to oil absorption imprinting, and the oil absorption surface of the oil absorption imprinting material is vertically exposed; and the camera is used for acquiring an image of the oil absorption side of the exposed oil absorption imprinting material, comparing the acquired image with a standard image in a database and analyzing the oil content in the film.
In general, the oil-absorbing material is a planar sheet structure, but in order to enable the oil content to be judged with higher resolution, the oil-absorbing imprint material of the present invention adopts a composite structure including a planar substrate and lattice-like projections on the substrate. Thus, under the external force extrusion, the grid-shaped protrusions can adsorb more grease, so that an obvious grease stain pattern is formed. The general plane oil absorption material can form a planar oil stain and is not suitable for judging the oil content, and the lattice-shaped pattern of the oil stain can accurately judge the oil content according to the thickness and the color depth of a lattice line, so that the detection of a camera is more accurate and convenient. This is also one of the points of the present invention.
Those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than others, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims, any of the claimed embodiments may be used in any combination.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.
Claims (5)
1. A method for preparing a film with uniform water absorption is characterized in that:
the raw material A is polyethylene and comprises the following two parts
A1: molecular weight 6.5X 106-8.5×106The polyethylene particles of (a);
a2: the density is 0.966-0.983g/cm3The polyethylene particles of (a);
the raw material B is paraffin oil; the raw material C is silicon dioxide nano particles with the diameter of 20-30 nm; the raw material D is 4, 4' -thiobis (6-tert-butyl-m-cresol);
step 1: the 4 raw materials are heated and mixed in batches: a first batch of material A1 and material D and half the weight of material B; adding the raw material A2 and the other half weight of the raw material B in a second batch; adding raw material C for the third batch;
step 2: injecting the mixed slurry into an extruder to extrude into a thick film;
and step 3: sequentially carrying out longitudinal stretching and transverse stretching on the thick film, wherein the stretching ratio is 6-7, obtaining a thin film, and extracting after the stretching is finished;
and 4, step 4: the film is conveyed to a two-dimensional stretching device, light transmittance abnormal points on the film are obtained, and a stretching area is determined according to the distribution of the abnormal points;
and 5: correspondingly controlling a two-dimensional stretching device to perform a film two-dimensional stretching process according to the determined stretching area;
step 6: moving the water spraying device to the position above the film for quantitative water spraying, forming a water layer on the surface of the film after the water spraying is finished, moving the water spraying device away, starting a light source and a camera for detection, and obtaining film images of the completion time of the water spraying and the standing time of 10 minutes, 30 minutes and 60 minutes, so as to determine an abnormal water absorption area of the film;
and 7: the film production and manufacturing process can be controlled in a feedback mode according to the distribution of the water absorption abnormal areas, and the method specifically comprises the following steps:
(1) if the abnormal water absorption areas are distributed irregularly in a large area, the production process has a large defect, and the production line should be stopped for maintenance;
(2) if the water absorption abnormal areas are distributed in the longitudinal direction, controlling a longitudinal stretching device of the two-dimensional stretching mechanism to longitudinally stretch the corresponding positions, and not stretching the rest positions; or stretching the rest positions without longitudinally stretching the corresponding positions;
(3) if the water absorption abnormal area is distributed in the transverse direction, controlling a transverse stretching device of the two-dimensional stretching mechanism to transversely stretch the corresponding position, and not stretching the rest positions; or stretching the rest positions without stretching the corresponding positions in the transverse direction;
and 8: and drying for 30 minutes, and coiling after drying.
2. The method of claim 1, wherein: the distance between the water spraying device and the film is less than 10 cm.
3. The method of claim 1, wherein: the grain diameter of the sprayed water drops is ensured to be 0.05-0.15 mm.
4. The method of claim 1, wherein: also comprises an oil content detection step.
5. A film having uniform water absorption, characterized in that: prepared using a process as claimed in any preceding claim.
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| CN110922906A (en) * | 2018-09-19 | 2020-03-27 | 琳得科株式会社 | Adhesive sheet for battery and lithium ion battery |
| CN111615422A (en) * | 2018-09-11 | 2020-09-01 | 株式会社Lg化学 | Crosslinked polyolefin separator and method for producing same |
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| CN106317466A (en) * | 2016-08-19 | 2017-01-11 | 南京林业大学 | Method for preparing lithium battery diaphragm by compounding nano-cellulose and nano-silicon dioxide |
| CN110291144A (en) * | 2017-02-09 | 2019-09-27 | 积水化学工业株式会社 | Synthetic resin microporous membrane and its manufacturing method, electrical storage device diaphragm and electrical storage device |
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