阅读说明：本技术 一种陶瓷涂覆pe复合型隔膜的制备方法 (A kind of preparation method of the compound diaphragm of ceramic coated PE ) 是由 高保清 舒均国 陈立新 高芳 于 2019-07-05 设计创作，主要内容包括：本发明公开了一种陶瓷涂覆PE复合型隔膜的制备方法,属于锂离子电池隔膜制备技术领域,包括以下步骤：采用锂离子电池PE隔膜为基体,在其两侧均匀涂覆厚度为1~3μm混有以下重量份的原料：纳米SiO<Sub>2</Sub>粉末1-3份、纳米Al<Sub>2</Sub>O<Sub>3</Sub>粉末1-3份、纳米TiO<Sub>2</Sub>粉末2-5份、PMMA颗粒2-5份及氧化β-环糊精0.01-0.03份、NMP0.01-0.03份作为溶剂的无机有机浆体,在80-100℃条件下热压10-15 min,取出后冷却,得到一种陶瓷涂覆PE复合型隔膜。本发明以气悬浮的动力方式,增加涂覆设备在涂层涂覆过程中的张力控制以及浆料的分布混合方式,解决涂覆层致密性、均匀性以及涂层结合力的技术问题。(The invention discloses a kind of preparation methods of compound diaphragm of ceramic coated PE, belong to lithium ion battery separator preparation technical field, the following steps are included: using lithium ion battery PE diaphragm for matrix, in its two sides, uniform coating thickness is 1 ~ 3 μm of raw material for being mixed with following parts by weight: Nano-meter SiO_2 2 1-3 parts of powder, nanometer Al 2 O 3 1-3 parts of powder, nano-TiO 2 2-5 parts of powder, 2-5 parts of PMMA particle and oxidation beta-cyclodextrin 0.01-0.03 parts, the NMP0.01-0.03 parts of inorganic organic slurries as solvent, hot pressing 10-15 min under the conditions of 80-100 DEG C is cooling after taking-up, obtains a kind of compound diaphragm of ceramic coated PE.The present invention is with the power mode of gas suspension, the technical issues of increasing the distributed rendering mode of tension force and slurry of the coating equipment in coating application procedures, solve coat compactness, uniformity and coating binding force.)

1. a kind of preparation method of the compound diaphragm of ceramic coated PE, which comprises the following steps:

Use lithium ion battery PE diaphragm for matrix, uniform coating thickness is 1 ~ 3 μm of original for being mixed with following parts by weight in its two sides Material: Nano-meter SiO_2₂1-3 parts of powder, nanometer Al₂O₃1-3 parts of powder, nano-TiO₂2-5 parts of powder, 2-5 parts of PMMA particle and oxidation 0.01-0.03 parts of beta-cyclodextrin, the NMP0.01-0.03 parts of inorganic organic slurries as solvent, hot pressing under the conditions of 80-100 DEG C 10-15 min, it is cooling after taking-up, obtain a kind of compound diaphragm of ceramic coated PE.

2. the preparation method of the compound diaphragm of ceramic coated PE according to claim 1, which is characterized in that PE diaphragm is applying Before covering, 8-10min is impregnated in ethanol, then after propylene acid dip 8-10min, is dried.

3. the preparation method of the compound diaphragm of ceramic coated PE according to claim 1, which is characterized in that Nano-meter SiO_2₂Powder 2 part, nanometer Al of end₂O₃2 parts of powder, nano-TiO₂3 parts of powder, 3 parts of PMMA particle and oxidation 0.02 part of beta-cyclodextrin, NMP0.02 Part.

4. the preparation method of the compound diaphragm of ceramic coated PE according to claim 1, which is characterized in that in 90 DEG C of conditions Lower hot pressing 12min.

5. the preparation method of the compound diaphragm of ceramic coated PE according to claim 1, which is characterized in that in coating procedure The coating equipment of use is equipped with gas suspension transmission system.

Technical field

The invention belongs to lithium ion battery separator preparation technical fields, are related to a kind of system of compound diaphragm of ceramic coated PE Preparation Method.

Background technique

One of the critical material that diaphragm is produced as lithium ion battery plays important influence to the actual performance of battery and makees With: on the one hand, diaphragm plays the role of electronic isolation, avoids inside battery that short circuit occurs；Another aspect diaphragm is ion transport Channel is provided, guarantees going on smoothly for electrochemical reaction.The rapid development in power vehicle field, to battery high power performance and Security performance has higher requirement, and diaphragm has played key effect to lithium-ion-power cell these two aspects performance.As power The key component of battery, diaphragm obstruct lithium ion transmitting by closed pore under runaway condition, prevent safety accident.

At present realize large-scale commercial production lithium ion battery separator be polyolefins diaphragm, with polyethylene (PE), Based on polypropylene (PP) monofilm and polyethylene/polypropylene/polyethylene (PE/PP/PE) composite membrane.Such diaphragm has resistance to organic It is electrolysed the advantages that fluidity, microcellular structure are uniform, mechanical strength is higher, but its wetability is poor, thermal stability low (such as PE film and PP About 135 DEG C and 165 DEG C respectively of the broken film temperature of film, there is the contraction of larger proportion at high temperature), therefore it is applied to large capacity Single battery safety is insufficient.Its thermal stability and electrolyte wetability are improved by modified diaphragm in the industry, such as coat it is organic- Inorganic ceramic particle (Al₂O₃、SiO₂、TiO₂) form composite diaphragm.Such diaphragm is prepared by mature coating apparatus, with Inorganic material resistant to high temperature protects polyolefin film, guarantees the integrality of battery diaphragm form under worst hot case, prevents battery short Thermal runaway caused by road, to improve the performance of safety and the quick charge and discharge of battery.Such as Jung passes through atomic layer deposition Technology deposited the ultra-thin Al that a layer thickness is about 6nm in PP micropore film surface₂O₃Functional layer obtains Ceramic Composite diaphragm, this Ceramic layer improves the heat resistance of PP film, while improving the lyophily of original PP basement membrane；Under the conditions of 4C rate charge-discharge, warp Discharge capacity can still keep 80% or so after crossing 1000 circulations.German Degussa company is by SiO₂、Al₂O₃It is blended together with adhesive Slurry, coated in Separion series diaphragm is prepared on non-woven fabrics basement membrane, which will not occur obviously to receive at 200 DEG C Contracting, has been applied to power example battery.

The production technology relative maturity of external composite diaphragm, and the country is still in starting in ceramic coating composite diaphragm field Stage, while also lacking the innovation of method and technique.Although common ceramic coating improves the resistance to of diaphragm to a certain extent Hot and battery security performance, it is also possible to bringing following new problem: (1) interface compatibility of organic-inorganic material is poor, There are dusting problems in composite diaphragm；(2) the pore structure control not enough optimization of ceramic layer, ceramic layer densification meeting plug-hole be not fine and close It is unobvious to the improved heat resistance of diaphragm etc..

Summary of the invention

It is an object of the invention to overcome defect existing in the prior art, a kind of compound diaphragm of ceramic coated PE is provided Preparation method, this method prepares the modified ceramic coating with hierarchical porous structure, passes through the three-dimensional netted porous grade of control The specific surface area that structure increases diaphragm material improves the affinity of electrolyte diaphragm material；And by research and development novel binders, change The bond strength of kind ceramic composition and diaphragm, and improve the conducting power of lithium ion.

Itself the specific technical proposal is:

A kind of preparation method of the compound diaphragm of ceramic coated PE, comprising the following steps:

Use lithium ion battery PE diaphragm for matrix, uniform coating thickness is 1 ~ 3 μm of original for being mixed with following parts by weight in its two sides Material: Nano-meter SiO_2₂1-3 parts of powder, nanometer Al₂O₃1-3 parts of powder, nano-TiO₂2-5 parts of powder, 2-5 parts of PMMA particle and oxidation 0.01-0.03 parts of beta-cyclodextrin, the NMP0.01-0.03 parts of inorganic organic slurries as solvent, hot pressing under the conditions of 80-100 DEG C 10-15 min, it is cooling after taking-up, obtain a kind of compound diaphragm of ceramic coated PE.

Further, PE diaphragm before coating, impregnates 8-10min in ethanol, then after propylene acid dip 8-10min, It is dried.

Further, Nano-meter SiO_2₂2 part, nanometer Al of powder₂O₃2 parts of powder, nano-TiO₂3 parts of powder, 3 parts of PMMA particle and 0.02 part, NMP0.02 parts of beta-cyclodextrin of oxidation.

Further, hot pressing 12min under the conditions of 90 DEG C.

Further, the coating equipment used in coating procedure is equipped with gas suspension transmission system.

Compared with prior art, the invention has the benefit that

1) with the power mode of gas suspension, increase the distribution of tension force and slurry of the coating equipment in coating application procedures The technical issues of hybrid mode, solution coat compactness, uniformity and coating binding force.

2) template with three-dimensional micropore structure and effective functional group are in composite ceramic layer (SiO₂、Al₂O₃、TiO₂) with The mechanism of action of the binding force of diaphragm.

3) system optimization three-dimensional micropore structure composite ceramic layer (SiO₂、Al₂O₃、TiO₂) with the combination process of PE P diaphragm, Set up the quantitative relationship between process conditions and membrane properties.

Specific embodiment

Technical solution of the present invention is described in more detail combined with specific embodiments below.