WO2022062326A1 - 锂电池隔膜、电化学装置、用于改善薄膜铸片横向厚度分布及模头节料的方法 - Google Patents

锂电池隔膜、电化学装置、用于改善薄膜铸片横向厚度分布及模头节料的方法 Download PDF

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WO2022062326A1
WO2022062326A1 PCT/CN2021/080288 CN2021080288W WO2022062326A1 WO 2022062326 A1 WO2022062326 A1 WO 2022062326A1 CN 2021080288 W CN2021080288 W CN 2021080288W WO 2022062326 A1 WO2022062326 A1 WO 2022062326A1
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Prior art keywords
joint
die head
die
thickness distribution
improving
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PCT/CN2021/080288
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English (en)
French (fr)
Inventor
程跃
朱小平
熊磊
庄志
虞少波
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上海恩捷新材料科技有限公司
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Publication of WO2022062326A1 publication Critical patent/WO2022062326A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/275—Recovery or reuse of energy or materials
    • B29C48/277—Recovery or reuse of energy or materials of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working

Definitions

  • the invention relates to the technical field of lithium battery separators, in particular to a lithium battery separator, an electrochemical device, a method for improving the lateral thickness distribution of a thin-film casting sheet and a die head material saving method.
  • wet lithium battery diaphragm mainly adopts extrusion casting process, that is, the required raw materials are extruded into sheet-like materials through a twin-screw extruder, and the sheet-like materials are cast and formed on a casting roll to facilitate further drawing in the subsequent process. Stretch the diaphragm to the desired thickness.
  • the material extruded from the extruder cannot be cast directly on the casting roll, and needs to be extruded into a sheet material of a certain thickness through a die structure of a certain shape.
  • the main process of wet-process lithium battery separator also includes MD/TD stretching, extraction, heat setting, and winding. Due to the biaxial stretching involved, the positions of the left and right ends of the thick sheet along the MD direction are bound to be clamped by chain clips in the stretching section, and the clamped thick sheet cannot be stretched and oriented according to the preset magnification. After the final release of the chain clip, it will be cut and removed to ensure the thickness uniformity of the final finished diaphragm. According to the existing process conditions and routes, the cut thick sheets cannot be recycled, which will not only cause great waste of raw materials, but also cause certain pollution to the environment.
  • the purpose of the present invention is to solve the problems of thickness uniformity, waste of raw materials and environmental pollution of finished diaphragms in the prior art.
  • the object of the present invention is to provide a kind of method that is used to improve the lateral thickness distribution of thin film castings and die head material, and described steps are as follows:
  • the first fluid extruded by the main extruder and the second fluid extruded by the auxiliary extruder enter the respective flow channels through the distributor of the die device, and finally merge and flow out from the die lip;
  • step (3) heat-setting, secondary edge trimming, material cutting, and backflow to the auxiliary extruder can be carried out, and the second fluid can be extruded again through the distributor of the die device into its flow channel.
  • the die head device includes a die head body, a die lip is installed at the bottom of the die head body, and a distributor is installed at the top of the die head body;
  • the distributor includes a first joint, a second joint, and a third joint , the first joint is located in the middle of the second joint and the third joint; a first open end is formed above the first joint, and the first open end is connected with the feeding pipe of the main extruder;
  • the second joint A second open end and a third open end are respectively formed above the middle of the joint and the third joint, and the second open end and the third open end are connected with the feeding pipe of the auxiliary main extruder;
  • the lower end of the first joint is connected with The first interface connected with the distributor, the lower end of the second joint is the second interface connected with the distributor, the lower end of the third joint is the third interface connected with the distributor; a first fluid distribution pipe, one end of which is connected with the distributor;
  • the first interface is connected, the other end of which is open, the first fluid distribution pipe
  • the internal flow channel of the die head body is a coat-hanger-shaped structure
  • the interior of the first fluid distribution pipe is a coat-hanger-shaped hollow.
  • the coat-hanger-shaped structure is preferred for better melt fluid flowability.
  • first joint, the second joint and the third joint are all provided with on-off valves.
  • the material cutting operation adopts a cutting machine
  • the auxiliary extruder is provided with a feeding hopper, which is connected with the pelletizer through a vacuum adsorption pipeline, and the pelletizer is connected with the traction roller, and the traction
  • the rollers are attached to MD/TD stretching equipment and/or heat setting equipment.
  • the purpose of using the traction roller is different from that of the prior art.
  • the prior art is connected to the equipment in the MD/TD stretching process or the heat setting process to allow the cut material (the cut part is mainly for auxiliary extrusion).
  • the raw material part extruded from the machine is rolled up by the action of the traction roller, so as to be collected and discarded, and the purpose of the present utility model here is equivalent to the function of circulation, using the traction roller to transfer the cut material flow through the vacuum
  • the adsorption pipeline enters the pelletizer.
  • the auxiliary extruder is further provided with an auxiliary feeding hopper.
  • the purpose of the additional auxiliary hopper is: if the melt index characteristics of the trimmings obtained after the TD stretching process or the heat setting process can no longer meet the requirements of the auxiliary extruder for the raw materials, they need to be granulated a second time.
  • the process of secondary granulation in addition to cutting the obtained edge material into the feeding hopper of the auxiliary extruder, it is also necessary to add new polyethylene raw materials to the auxiliary feeding hopper of the auxiliary extruder, so that the feeding hopper and the auxiliary feeding The PE mixing in the hopper finally obtains the PE raw material that can meet the requirements of the auxiliary extruder.
  • the pelletizer cuts the offcuts into elongated particles with a diameter of 1-3 mm and an aspect ratio of less than or equal to 10.
  • the extrusion volume of the auxiliary extruder is 20% of that of the main extruder.
  • melt index of the fluid extruded by the main extruder and the auxiliary extruder is consistent, ranging from 0.1 to 10kg/10min (2.16kg load).
  • the transverse thickness distribution tolerance of the diaphragm product with uniform transverse thickness distribution is ⁇ 1 ⁇ m.
  • the purpose of the present invention is also to provide a lithium battery separator, which is prepared by the above-mentioned method for improving the lateral thickness distribution of the thin film casting and the material saving of the die head.
  • the purpose of the present invention is also to provide an electrochemical device, using the separator prepared by the above method as a component for separating the positive and negative electrodes of the battery.
  • the present invention provides a method for improving the lateral thickness distribution of thin film castings and the material saving of the die head, which can significantly improve the thickness uniformity of the finished diaphragm;
  • the present invention can also recycle the trimming obtained after the TD stretching process, thereby further solving the problems of raw material waste and environmental pollution under the condition of ensuring the thickness uniformity of the finished diaphragm;
  • the present invention can also recycle and utilize the trimmings obtained after the heat-setting process, thereby further saving raw materials under the condition of ensuring the thickness uniformity of the finished diaphragm;
  • an auxiliary feeding hopper can also be set on the auxiliary extruder to carry out the operation of secondary granulation, so as to continuously recover and supplement the PE raw material method that meets the requirements of the auxiliary extruder.
  • the purpose of the present invention has been achieved, and it is more conducive to the application of industrial continuity;
  • a development valve can also be set on the joint of the distributor, so as to realize the flexible switching of the feeding mode, and there is an additional way of stopping the feeding.
  • FIG. 1 is an internal schematic diagram of a die device according to an embodiment of the present invention.
  • FIG. 2 is a flow chart of a method for improving the lateral thickness distribution of thin film castings and the material saving of the die according to an embodiment of the present invention
  • a die device structure of an embodiment involved in the method for improving the lateral thickness distribution of a thin film casting sheet and the die head material saving method of the present invention includes a die head body, and a die head body is installed at the bottom of the die head body.
  • a distributor 1 is installed on the top of the die body; the distributor 1 includes a first joint, a second joint and a third joint, and the first joint is located between the second joint and the third joint; the first joint is located between the second joint and the third joint; A first open end is formed above a joint, and the first open end is connected with the feeding pipe of the main extruder, and the main extruder is provided with a feeding hopper; the upper part of the middle of the second joint and the third joint are respectively The second open end and the third open end are formed, and the second open end and the third open end are connected with the feeding pipe of the auxiliary main extruder; the lower end of the first joint is the first interface connected with the distributor, The lower end of the second joint is the second interface connected with the distributor, the lower end of the third joint is the third interface connected with the distributor; a first fluid distribution pipe, one end of which is connected with the first interface, and its The other end is open, the first fluid distribution pipe is a molding channel, and the interior is hollow, forming the first
  • the raw materials used in the main extruder are mineral oil with a viscosity average molecular weight of 600,000 and a kinematic viscosity of 51 at 40°C, and 0.5% antioxidant is added as a processing aid.
  • the raw materials used in the auxiliary extruder are melt index 1.86kg/ 10min (2.16kg load) of low density polyethylene, and also add 0.5% antioxidant as a processing aid.
  • the raw materials were mixed evenly in their respective mixing hoppers, gradually added to the extruder, and flowed out through the die lips of the die head device described in Example 1. After stretching, trimming, extraction, heat setting, trimming and other processes, the average thickness of the final rolling diaphragm is 9um, and the transverse thickness distribution tolerance is ⁇ 0.5um.
  • the raw materials used in the main extruder are mineral oil with a viscosity average molecular weight of 600,000 and a kinematic viscosity of 51 at 40°C, and 0.5% antioxidant is added as a processing aid.
  • the raw materials used in the auxiliary extruder It is low density polyethylene with a melt index of 1.86kg/10min (2.16kg load), and 0.5% antioxidant is also added as a processing aid.
  • the raw materials were mixed evenly in their respective mixing hoppers, gradually added to the extruder, and flowed out through the die lips of the die head device described in Example 1.
  • the edge material obtained by stretching, trimming and trimming is transferred to the vacuum adsorption pipeline through the traction roller, and then enters the pelletizer to be cut into long-shaped particles with a diameter of 1mm and an aspect ratio of 10, and then enters the auxiliary extruder for secondary extrusion.
  • the diaphragm is extracted, heat-set, and then trimmed for a second time.
  • the trimmings obtained from trimming are drawn back into the auxiliary extruder in the same manner as above for secondary extrusion.
  • the average thickness of the diaphragm obtained by final winding is 9um
  • the lateral thickness distribution tolerance is ⁇ 0.5um
  • the loss of edge material is 0.
  • the raw materials used in the main extruder are mineral oil with a viscosity average molecular weight of 600,000 and a kinematic viscosity of 51 at 40°C, and 0.5% antioxidant is added as a processing aid.
  • the raw materials used in the auxiliary extruder are melt index 1.86kg/ 10min (2.16kg load) of low density polyethylene, and also add 0.5% antioxidant as a processing aid.
  • the raw materials were mixed evenly in their respective mixing hoppers, gradually added to the extruder, and flowed out through the die lips of the die head device described in Example 1.
  • the edge material obtained by stretching, trimming and trimming is transferred to the vacuum adsorption pipeline through the traction roller and enters the pelletizer to be cut into long-shaped particles with a diameter of 3mm and an aspect ratio of 5, and then enters the auxiliary extruder for secondary extrusion.
  • the diaphragm is extracted, heat-set, and then trimmed for a second time.
  • the trimmings obtained from trimming are drawn back into the auxiliary extruder in the same manner as above for secondary extrusion.
  • the average thickness of the final rolled diaphragm is 9um, the lateral thickness distribution tolerance is ⁇ 1um, and the scrap loss is 0.
  • Another embodiment of the die device structure involved in the method for improving the lateral thickness distribution of a thin film cast sheet and the die head material saving method of the present invention includes a die head body, and a die lip 5 is installed at the bottom of the die head body.
  • a distributor 1 is installed on the top of the body, and the internal flow channel of the die body is a coat hanger-shaped structure; the distributor 1 includes a first joint, a second joint, and a third joint, and the first joint is located between the second joint and the In the middle of the third joint; a first open end is formed above the first joint, and the first open end is connected with the feeding pipe of the main extruder, which is provided with a feeding hopper; the second joint A second open end and a third open end are respectively formed above the middle of the joint and the third joint, and the second open end and the third open end are connected with the feeding pipe of the auxiliary main extruder; the lower end of the first joint is connected with The first interface connected with the distributor, the lower end of the second joint is the second interface
  • the auxiliary extruder is provided with a feeding hopper, which is connected with the pelletizer through a vacuum adsorption pipeline.
  • the pelletizer is connected with a traction roller, and a traction roller is provided at the MD/TD stretching process and the heat setting process. It is connected with MD/TD stretching equipment and heat-setting equipment.
  • the auxiliary extruder is also provided with an auxiliary feeding hopper for adding new polyethylene raw materials, so that the PE in the feeding hopper and the auxiliary feeding hopper is mixed and finally obtained. PE raw material that can meet the requirements of auxiliary extruder.
  • the structure of the die head device in the comparative example includes a die head body, a die lip 5 is installed at the bottom of the die head body, and a distributor 1 is installed at the top of the die head body; Three joints, the first joint is located between the second joint and the third joint; a first open end is formed above the first joint, and the first open end is connected with the feeding pipe of the main extruder, and the main The extruder is provided with a feeding hopper; a second open end and a third open end are respectively formed above the middle of the second joint and the third joint, and the second open end and the third open end are connected to the auxiliary main extruder.
  • the feed pipe is connected; the lower end of the first joint is the first interface connected with the distributor, the lower end of the second joint is the second interface connected with the distributor, and the lower end of the third joint is the first interface connected with the distributor Three ports; a first fluid distribution pipe, one end of which is connected to the first port, the other end is open, the first fluid distribution pipe is a molding channel, the interior is hollow, forming the main extruder flow Channel 3; a second fluid distribution pipe, one end of which is connected to the second interface, and the other end is open; another second fluid distribution pipe, one end of which is connected to the third interface, and the other end is open shape, respectively form the auxiliary extruder flow channel 2; the distance from the opening of the distribution pipe to the die lip 5 accounts for one-third of the height of the entire die body, and the two fluids merge to form the flow channel confluence area 4; the The first joint, the second joint and the third joint are all provided with on-off valves, and the valves of the second joint and the third joint are closed at this time
  • the die lips of the above-mentioned device meet and flow out, and after casting, a thick sheet with a thickness of about 1mm is formed, and then the scrap obtained by MD/TD synchronous stretching, trimming and trimming is collected and weighed, and the weight is recorded as M1. After stretching, the separator is extracted, heat-set, and then trimmed for a second time. The trimmings obtained from trimming are collected and weighed. The final calculation shows that (M1+M2)/M0 is equal to 20%, the average thickness of the diaphragm obtained by winding is 9um, and the lateral thickness distribution tolerance is ⁇ 1.5um.

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Abstract

本发明涉及锂电池隔膜技术领域，具体公开了一种用于改善薄膜铸片横向厚度分布及模头节料的方法，所述步骤如下：主挤出机挤出的第一流体、辅挤出机挤出的第二流体通过模头装置的分配器进入各自流道，并最终汇合，从模唇流出；再经铸片，MD/TD拉伸后，进行一次切边、切料、回流至辅挤出机后再次挤出第二流体通过模头装置的分配器进入其流道；后经萃取，热定型，收卷，得到横向厚度分布均匀的隔膜产品。解决了现有技术中成品隔膜的厚度均匀性、原材料浪费和环境污染的问题。

Description

锂电池隔膜、电化学装置、用于改善薄膜铸片横向厚度分布及模头节料的方法 技术领域
本发明涉及锂电池隔膜技术领域，具体涉及锂电池隔膜、电化学装置、用于改善薄膜铸片横向厚度分布及模头节料的方法。
背景技术
湿法锂电隔膜的生产主要采用挤出流延工艺，即通过双螺杆挤出机将所需原料挤出成片状材料，片状材料在流延辊上铸片成型，以便于后道进一步拉伸成所需厚度的隔膜。一般来说，从挤出机里挤出的材料无法直接在流延辊上流延成型，需要通过一定形状的模头结构挤出成一定厚度的片状材料。
湿法锂电隔膜主要工艺除了挤出铸片以外，还包括MD/TD拉伸，萃取，热定型，收卷。由于涉及到双向拉伸，厚片沿MD方向左右两端端部的位置在拉伸段必然会受到链夹夹持，受到夹持的厚片部位无法按照预先设定的倍率进行拉伸取向，最终脱离链夹后会被裁切去除，以保证最终成品隔膜的厚度均匀性。按照现有的工艺条件及路线，被裁切的厚片是无法循环回收利用的，这不仅会造成原材料的极大浪费，还会对环境造成一定的污染。
发明内容
有鉴于此，本发明的目的在于解决现有技术中成品隔膜的厚度均 匀性、原材料浪费和环境污染的问题。
为达到上述目的，本发明的技术方案是这样实现的：
本发明的目的是提供一种用于改善薄膜铸片横向厚度分布及模头节料的方法，所述步骤如下：
(1)主挤出机挤出的第一流体、辅挤出机挤出的第二流体通过模头装置的分配器进入各自流道，并最终汇合，从模唇流出；
(2)再经铸片，MD/TD拉伸后，进行一次切边、切料、回流至辅挤出机后再次挤出第二流体通过模头装置的分配器进入其流道；
(3)后经萃取，热定型，收卷，得到横向厚度分布均匀的隔膜产品。
进一步地，所述步骤(3)热定型后还可以进行二次切边、切料、回流至辅挤出机后再次挤出第二流体通过模头装置的分配器进入其流道。
更进一步地，所述模头装置包括模头本体，模头本体的底部安装有模唇，模头本体的顶部安装有分配器；所述分配器包括第一接头、第二接头、第三接头，所述第一接头位于第二接头和第三接头中间；所述第一接头上方成型有第一开口端，所述第一开口端与主挤出机供料管连接；所述第二接头和第三接头中间上方均分别成型有第二开口端、第三开口端，所述第二开口端、第三开口端与辅主挤出机供料管连接；所述第一接头下端为与分配器相连的第一接口，所述第二接头下端为与分配器相连的第二接口，所述第三接头下端为与分配器相连的第三接口；一个第一流体分配管，其中一端与该第一接口完成连接， 其另一端成开口状，所述第一流体分配管为一个成型渠道，内部呈中空状；一个第二流体分配管，其中一端与该第二接口完成连接，其另一端成开口状；另一个第二流体分配管，其中一端与该第三接口完成连接，其另一端成开口状；所述分配管开口到模唇的距离占整个所述模头本体高度的不超过三分之一，另外三分之二属于各自的流道。
具体地，所述模头本体内部流道为衣架形结构，所述第一流体分配管内部呈衣架形中空状。这里，优选衣架形结构是为了更好的熔融流体流动性。
具体地，所述第一接头、第二接头、第三接头上均设有开关阀门。
更进一步地，所述切料操作采用切料机，所述辅挤出机设有加料斗，其通过真空吸附管道与切粒机相连，所述切粒机与牵引滚轮相连接，所述牵引滚轮与MD/TD拉伸设备和/或热定型设备相连接。这里，牵引滚轮的使用目的与现有技术不同，现有技术在MD/TD拉伸工序或热定型工序中与设备相连接是为了让裁切下来的料(所裁切的部分主要为辅挤出机挤出的原料部分)通过牵引滚轮的作用进行收卷，从而收集起来进行废弃，而本实用新型此处的目的在于相当于流转的作用，利用牵引滚轮将裁切下来的料流转过真空吸附管道进入切粒机。
具体地，所述辅挤出机还设有辅加料斗。这里，附加辅加料斗的目的在于：如TD拉伸工序或热定型工序后裁切所得边料熔指特性已无法满足辅挤出机对于原料的要求，则需要对其进行二次造粒，二次造粒的过程中除了裁切所得边料进入所述辅挤出机的加料斗外，还需往辅挤出机的辅加料斗中加入新的聚乙烯原料，这样加料斗与辅加料 斗中PE混合最终得到可以满足辅挤出机要求的PE原料。
具体地，所述切粒机将边料切至直径1～3mm，长径比小于等于10的长条形粒子。
进一步地，所述辅挤出机的挤出量为主挤出机的20％。
进一步地，所述主挤出机和辅挤出机所挤出的流体熔指一致，在0.1～10kg/10min(2.16kg载荷)。
进一步地，所述横向厚度分布均匀的隔膜产品的横向厚度分布公差≤±1μm。
本发明的目的还提供一种锂电池隔膜，采用上述用于改善薄膜铸片横向厚度分布及模头节料的方法制备而成。
本发明的目的还提供一种电化学装置，采用上述方法制备出的隔膜作为隔离电池正、负极的元件。
本发明有益效果如下：
1)本发明提供一种用于改善薄膜铸片横向厚度分布及模头节料的方法，采用该方法可以明显提升成品隔膜的厚度均匀性；
2)本发明还可以回收利用TD拉伸工序后裁切所得边料，从而在保证成品隔膜的厚度均匀性的情况下，进一步解决原材料浪费和环境污染的问题；
3)本发明还可以回收利用热定型工序后裁切所得边料，从而在保证成品隔膜的厚度均匀性的情况下，更进一步的节省原材料；
4)本发明还可以在辅挤出机上设置辅加料斗，进行二次造粒的操作，从而可以源源不断的进行回收+补充形成满足辅挤出机要求的 PE原料方法，可以不停机生产且一直实现本发明的目的，更有利于工业连续化的应用；
5)本发明还可以在分配器接头上设置开发阀门，从而实现进料方式的灵活切换，也多了一种停止进料的方式。
附图说明
图1为本发明一种实施方式的模头装置的内部示意图；
图2为本发明一种实施方式的种用于改善薄膜铸片横向厚度分布及模头节料的方法流程图；
元件标号说明
1    分配器
2    辅挤出机流道
3    主挤出机流道
4    流道汇合区域
5    模唇
6    收卷工序
7    主挤出机
8    辅挤出机
9    模头本体
10   铸片工序
11   MD/TD拉伸工序
12   萃取工序
13   热定型工序
A    一次切边操作
B    二次切边操作
具体实施方式
以下将通过实施例结合附图对本发明进行详细描述。应当理解的是，此处所描述的实施例仅用于说明和解释本发明，并不用于限制本发明。
实施例1
如图1所示，本发明用于改善薄膜铸片横向厚度分布及模头节料的方法中涉及的一种实施方式的模头装置结构，包括模头本体，模头本体的底部安装有模唇5，模头本体的顶部安装有分配器1；所述分配器1包括第一接头、第二接头、第三接头，所述第一接头位于第二接头和第三接头中间；所述第一接头上方成型有第一开口端，所述第一开口端与主挤出机供料管连接，所述主挤出机设有加料斗；所述第二接头和第三接头中间上方均分别成型有第二开口端、第三开口端，所述第二开口端、第三开口端与辅主挤出机供料管连接；所述第一接头下端为与分配器相连的第一接口，所述第二接头下端为与分配器相连的第二接口，所述第三接头下端为与分配器相连的第三接口；一个第一流体分配管，其中一端与该第一接口完成连接，其另一端成开口状，所述第一流体分配管为一个成型渠道，内部呈中空状，形成主挤出机流道3；一个第二流体分配管，其中一端与该第二接口完成连接，其另一端成开口状；另一个第二流体分配管，其中一端与该第三接口完成连接，其另一端成开口状，分别形成辅挤出机流道2；所述分配管开口到模唇5的距离占整个所述模头本体高度的三分之一，两种流体汇合形成流道汇合区域4。
实施例2
主挤出机所用原料分别为粘均分子量为60万和40℃运动粘度为51的矿物油，另外添加0.5％的抗氧剂作为加工助剂，辅挤出机所用原料为熔指1.86kg/10min(2.16kg载荷)的低密度聚乙烯，同时也添加0.5％的抗氧剂作为加工助剂。原料分别在各自的混合料斗中混合均匀，逐步加入挤出机，经实施例1所述模头装置的模唇汇合流出，铸片后形成厚度约1mm的厚片，再经MD/TD同步拉伸、裁边、萃取、热定型、裁边等工序后最终收卷所得隔膜平均厚度为9um，横向厚度分布公差为±0.5um。
实施例3
如图2所示，主挤出机所用原料分别为粘均分子量为60万和40℃运动粘度为51的矿物油，另外添加0.5％的抗氧剂作为加工助剂，辅挤出机所用原料为熔指1.86kg/10min(2.16kg载荷)的低密度聚乙烯，同时也添加0.5％的抗氧剂作为加工助剂。原料分别在各自的混合料斗中混合均匀，逐步加入挤出机，经实施例1所述模头装置的模唇汇合流出，铸片后形成厚度约1mm的厚片，再经MD/TD同步拉伸、裁边、裁边所得边料通过牵引滚轮流转至真空吸附管道进入切粒机切成直径1mm，长径比为10的长条形粒子，再进入辅挤出机进行二次挤出。拉伸后，隔膜进行萃取，热定型，热定型之后进行二次裁边，裁边所得边料经上述同样的方式经牵引回流进入辅挤出机进行二次挤出。最终收卷所得隔膜平均厚度为9um，横向厚度分布公差为±0.5um，边料损耗为0。
实施例4
主挤出机所用原料分别为粘均分子量为60万和40℃运动粘度为51的矿物油，另外添加0.5％的抗氧剂作为加工助剂，辅挤出机所用原料为熔指1.86kg/10min(2.16kg载荷)的低密度聚乙烯，同时也添 加0.5％的抗氧剂作为加工助剂。原料分别在各自的混合料斗中混合均匀，逐步加入挤出机，经实施例1所述模头装置的模唇汇合流出，铸片后形成厚度约1mm的厚片，再经MD/TD同步拉伸、裁边、裁边所得边料通过牵引滚轮流转至真空吸附管道进入切粒机切成直径3mm，长径比为5的长条形粒子，再进入辅挤出机进行二次挤出。拉伸后，隔膜进行萃取，热定型，热定型之后进行二次裁边，裁边所得边料经上述同样的方式经牵引回流进入辅挤出机进行二次挤出。最终收卷所得隔膜平均厚度为9um，横向厚度分布公差为±1um，边料损耗为0。
实施例5
本发明用于改善薄膜铸片横向厚度分布及模头节料的方法中涉及的另一种实施方式的模头装置结构，包括模头本体，模头本体的底部安装有模唇5，模头本体的顶部安装有分配器1，所述模头本体内部流道为衣架形结构；所述分配器1包括第一接头、第二接头、第三接头，所述第一接头位于第二接头和第三接头中间；所述第一接头上方成型有第一开口端，所述第一开口端与主挤出机供料管连接，所述主挤出机设有加料斗；所述第二接头和第三接头中间上方均分别成型有第二开口端、第三开口端，所述第二开口端、第三开口端与辅主挤出机供料管连接；所述第一接头下端为与分配器相连的第一接口，所述第二接头下端为与分配器相连的第二接口，所述第三接头下端为与分配器相连的第三接口；一个第一流体分配管，其中一端与该第一接口完成连接，其另一端成开口状，所述第一流体分配管为一个成型渠道，内部呈衣架形中空状，形成主挤出机流道3；一个第二流体分配管，其中一端与该第二接口完成连接，其另一端成开口状；另一个第二流体分配管，其中一端与该第三接口完 成连接，其另一端成开口状，分别形成辅挤出机流道2；所述分配管开口到模唇5的距离占整个所述模头本体高度的四分之一，两种流体汇合形成流道汇合区域4。
所述辅挤出机设有加料斗，其通过真空吸附管道与切粒机相连，所述切粒机与牵引滚轮相连接，在MD/TD拉伸工序及热定型工序处均设有牵引滚轮与MD/TD拉伸设备和热定型设备相连接，此外，所述辅挤出机还设有辅加料斗，用于加入新的聚乙烯原料，这样加料斗与辅加料斗中PE混合最终得到可以满足辅挤出机要求的PE原料。
对比例
对比例中模头装置的结构包括模头本体，模头本体的底部安装有模唇5，模头本体的顶部安装有分配器1；所述分配器1包括第一接头、第二接头、第三接头，所述第一接头位于第二接头和第三接头中间；所述第一接头上方成型有第一开口端，所述第一开口端与主挤出机供料管连接，所述主挤出机设有加料斗；所述第二接头和第三接头中间上方均分别成型有第二开口端、第三开口端，所述第二开口端、第三开口端与辅主挤出机供料管连接；所述第一接头下端为与分配器相连的第一接口，所述第二接头下端为与分配器相连的第二接口，所述第三接头下端为与分配器相连的第三接口；一个第一流体分配管，其中一端与该第一接口完成连接，其另一端成开口状，所述第一流体分配管为一个成型渠道，内部呈中空状，形成主挤出机流道3；一个第二流体分配管，其中一端与该第二接口完成连接，其另一端成开口状；另一个第二流体分配管，其中一端与该第三接口完成连接，其另一端成开口状，分别形成辅挤出机流道2；所述分配管开口到模唇5的距离占整个所述模头本体高度的三分之 一，两种流体汇合形成流道汇合区域4；所述第一接头、第二接头、第三接头上均设有开关阀门，此时关闭第二接头、第三接头的阀门。
这里，只有一种流体，该流体为主挤出机供料管来的粘均分子量为60万和40℃运动粘度为51的矿物油、熔指1.86kg/10min(2.16kg载荷)的低密度聚乙烯，两种原料的总重量记为M0，以及添加0.5％的抗氧剂作为加工助剂。
经上述装置模唇汇合流出，铸片后形成厚度约1mm的厚片，再经MD/TD同步拉伸、裁边、裁边所得边料收集称重，重量记为M1。拉伸后，隔膜进行萃取，热定型，热定型之后进行二次裁边，裁边所得边料收集称重，重量记为M2。最终计算得到(M1+M2)/M0等于20％，收卷所得隔膜平均厚度为9um，横向厚度分布公差为±1.5um。
从实施例2、3、4和对比例对比可以看出，通过主挤出机和辅挤出机的同步挤出，并经分配器和流道调汇合及各道裁切料的回收后，边料的损耗可以完全消除，另外可以显著提升产品横向厚度的均匀性。
以上涉及到公知常识的内容不作详细描述，本领域的技术人员能够理解。
以上所述仅为本发明的一些具体实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。

Claims (13)

  1. 一种用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于，所述步骤如下：
    (1)主挤出机挤出的第一流体、辅挤出机挤出的第二流体通过模头装置的分配器进入各自流道，并最终汇合，从模唇流出；
    (2)再经铸片，MD/TD拉伸后，进行一次切边、切料、回流至辅挤出机后再次挤出第二流体通过模头装置的分配器进入其流道；
    (3)后经萃取，热定型，收卷，得到横向厚度分布均匀的隔膜产品。
  2. 根据权利要求1所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述步骤(3)热定型后还可以进行二次切边、切料、回流至辅挤出机后再次挤出第二流体通过模头装置的分配器进入其流道。
  3. 根据权利要求1或2所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述模头装置包括模头本体，模头本体的底部安装有模唇，模头本体的顶部安装有分配器；所述分配器包括第一接头、第二接头、第三接头，所述第一接头位于第二接头和第三接头中间；所述第一接头上方成型有第一开口端，所述第一开口端与主挤出机供料管连接；所述第二接头和第三接头中间上方均分别成型有第二开口端、第三开口端，所述第二开口端、第三开口端与辅主挤出机供料管连接；所述第一接头下端为与分配器相连的第一接 口，所述第二接头下端为与分配器相连的第二接口，所述第三接头下端为与分配器相连的第三接口；一个第一流体分配管，其中一端与该第一接口完成连接，其另一端成开口状，所述第一流体分配管为一个成型渠道，内部呈中空状；一个第二流体分配管，其中一端与该第二接口完成连接，其另一端成开口状；另一个第二流体分配管，其中一端与该第三接口完成连接，其另一端成开口状；所述分配管开口到模唇的距离占整个所述模头本体高度的不超过三分之一。
  4. 根据权利要求3所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述模头本体内部流道为衣架形结构，所述第一流体分配管内部呈衣架形中空状。
  5. 根据权利要求3所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述第一接头、第二接头、第三接头上均设有开关阀门。
  6. 根据权利要求1或2所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述切料操作采用切料机，所述辅挤出机设有加料斗，其通过真空吸附管道与切粒机相连，所述切粒机与牵引滚轮相连接，所述牵引滚轮与MD/TD拉伸设备和/或热定型设备相连接。
  7. 根据权利要求6所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述辅挤出机还设有辅加料斗。
  8. 根据权利要求6所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述切粒机将边料切至直径1～3mm， 长径比小于等于10的长条形粒子。
  9. 根据权利要求1所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述辅挤出机的挤出量为主挤出机的20％。
  10. 根据权利要求1所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述主挤出机和辅挤出机所挤出的流体熔指一致，在0.1～10kg/10min(2.16kg载荷)。
  11. 根据权利要求1所述的用于改善薄膜铸片横向厚度分布及模头节料的方法，其特征在于：所述横向厚度分布均匀的隔膜产品的横向厚度分布公差≤±1μm。
  12. 一种锂电池隔膜，其特征在于：采用如权利要求1～11用于改善薄膜铸片横向厚度分布及模头节料的方法制备而成。
  13. 一种电化学装置，其特征在于：采用如权利要求12所述的隔膜。
PCT/CN2021/080288 2020-09-27 2021-03-11 锂电池隔膜、电化学装置、用于改善薄膜铸片横向厚度分布及模头节料的方法 WO2022062326A1 (zh)

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