阅读说明：本技术 一种一维纳米线改性聚合物隔膜及其制备方法与应用 (A kind of polymer-modified diaphragm of one-dimensional nano line and the preparation method and application thereof ) 是由 王艳杰 邓春林 洪佳丹 何志欢 于 2019-08-27 设计创作，主要内容包括：本发明公开了一种一维纳米线改性聚合物隔膜及其制备方法与应用。所述制备方法为：(1)将一维纳米线分散于石蜡油中,然后加入硅烷偶联剂,在20～140℃下反应10～120min,得到分散液,过滤,得到固体粉末；(2)在220～240℃下将聚合物颗粒熔融,然后加入步骤(1)的分散液或固体粉末,反应10～120min；(3)采用湿法或干法单拉法制膜,得到一维纳米线改性聚合物隔膜。制得的隔膜安全性好、抗穿刺强度和拉伸强度高,具有较好的耐热性、孔隙率和离子电导率,可应用于锂电池领域。(The invention discloses polymer-modified diaphragms of a kind of one-dimensional nano line and the preparation method and application thereof.The preparation method is that: (1) it disperses one-dimensional nano line in paraffin oil, silane coupling agent is then added, 10~120min is reacted at 20~140 DEG C, obtains dispersion liquid, filter, obtain solid powder；(2) by melting of polymer pellets at 220~240 DEG C, the dispersion liquid or solid powder of step (1) is then added, reacts 10~120min；(3) it is film-made using wet process or dry method list daraf(reciprocal of farad), obtains the polymer-modified diaphragm of one-dimensional nano line.Diaphragm safety obtained is good, punctured resistance and tensile strength are high, has preferable heat resistance, porosity and ionic conductivity, can be applied to field of lithium.)

1. a kind of preparation method of the polymer-modified diaphragm of one-dimensional nano line, which comprises the following steps:

(1) disperse one-dimensional nano line in paraffin oil, silane coupling agent be then added, at 20~140 DEG C react 10~ 120min obtains silane coupler modified one-dimensional nano line dispersion liquid；

(2) by melting of polymer pellets at 220~240 DEG C, the silane coupler modified 1-dimention nano of step (1) is then added Line dispersion liquid reacts 10~120min, obtains the polymer-modified mixed liquor of one-dimensional nano line；

(3) the polymer-modified mixed liquor of one-dimensional nano line is filmed using wet process, it is polymer-modified obtains one-dimensional nano line Diaphragm；

Wherein, step (2) polymer is in polyethylene, polypropylene, polyethylene terephthalate and Kynoar It is at least one；

Silane coupler modified one-dimensional nano line in the polymer beads and silane coupler modified one-dimensional nano line dispersion liquid Mass ratio be 10:1~1:10.

2. a kind of preparation method of the polymer-modified diaphragm of one-dimensional nano line, which comprises the following steps:

(1) disperse one-dimensional nano line in paraffin oil, silane coupling agent be then added, at 20~140 DEG C react 10~ 120min obtains silane coupler modified one-dimensional nano line dispersion liquid；Filtering, obtains silane coupler modified one-dimensional nano line；

(2) by melting of polymer pellets at 220~240 DEG C, the silane coupler modified 1-dimention nano of step (1) is then added Line reacts 10~120min, obtains the polymer-modified mixture of one-dimensional nano line；

(3) the polymer-modified mixture of one-dimensional nano line is filmed using dry method list daraf(reciprocal of farad), it is modified obtains one-dimensional nano line Membrane for polymer；

Wherein, the polymer is at least one in polyethylene, polypropylene, polyethylene terephthalate and Kynoar Kind；

The mass ratio of the polymer beads and silane coupler modified one-dimensional nano line is 10:1~1:10.

3. a kind of preparation method of the polymer-modified diaphragm of one-dimensional nano line according to claim 1 or claim 2, which is characterized in that Step (1) one-dimensional nano line is one-dimensional carbon nanotube, one-dimensional hydroxyapatite nano line, one-dimensional concave convex rod nano wire, one Tie up one or more of Kocide SD nano wire, one-dimensional silica white nano-wire and one-dimensional silver nanowires, a wiener The length of rice noodles is 50~3000nm, and width is 10~40nm.

4. the preparation method of the polymer-modified diaphragm of a kind of one-dimensional nano line according to claim 3, which is characterized in that step (1) mass ratio of the silane coupling agent and one-dimensional nano line is (0.0001~2): 1；The one-dimensional nano line and paraffin oil Mass ratio is (0.01~1): (0.01~1).

5. the preparation method of the polymer-modified diaphragm of a kind of one-dimensional nano line according to claim 4, which is characterized in that step (1) silane coupling agent is one or more of KH550, KH560 and KH570；The silane coupling agent with it is one-dimensional The mass ratio (0.11~2) of nano wire: 1.

6. the preparation method of the polymer-modified diaphragm of a kind of one-dimensional nano line according to claim 4, which is characterized in that step (1) mode of the dispersion is stirring or ultrasonic vibration, and the speed of agitator is 8000~10000r/min, the ultrasonic vibration Power be 400~500W；The jitter time be 0.1~for 24 hours, temperature be 20~140 DEG C；

Step (1) reaction temperature is 20~120 DEG C；Reaction time is 10~60min；Step (2) reaction time is 10~20min.

7. the preparation method of the polymer-modified diaphragm of a kind of one-dimensional nano line according to claim 1, which is characterized in that step (2) polymer beads and silane coupler modified one-dimensional nano line in silane coupler modified one-dimensional nano line dispersion liquid Mass ratio is 6~10:1.

8. the preparation method of the polymer-modified diaphragm of a kind of one-dimensional nano line according to claim 2, which is characterized in that step (2) mass ratio of the polymer beads and silane coupler modified one-dimensional nano line is 5~10:1.

9. a kind of polymer-modified diaphragm of one-dimensional nano line made from any one of claim 1~8 the method.

10. a kind of application of the polymer-modified diaphragm of one-dimensional nano line described in claim 9 in field of lithium ion battery.

Technical field

The invention belongs to new energy materials fields, and in particular to a kind of polymer-modified diaphragm of one-dimensional nano line and its preparation Method and application.

Background technique

With its energy density, the high, electrical property excellent with voltage height etc. that have extended cycle life is considered as most having to lithium ion battery One of new energy power form of development prospect, and become the research hotspot of current two battery eliminator, it is widely used in mobile phone, portable The fields such as formula computer, camera, video camera and electric car, electric bicycle, large-sized power power supply.The structure of lithium battery In, though diaphragm is not engaged in cell reaction but crucial one of interior layer assembly.Lithium ion battery separator is usually porous poly- Object film is closed, connects and separates anode and negative electrode material, be the insulator of electronics, but allow lithium ion quickly through thus complete At quick transmission of the lithium ion between positive and negative anodes during charge discharge, the superiority and inferiority of performance decides the boundary of battery The performance of face structure and interior barrier film, directly affects the characteristics such as the capacity, cycle performance and security performance of battery, therefore every The superiority and inferiority of film properties plays the role of the comprehensive performance of raising lithium ion battery very important.

Generally speaking, lithium ion battery separator material need to have following characteristic: hot closing property, punctured resistance, machinery Intensity, thermal dimensional stability, electronic isolation and ionic conductivity, electrolyte wettability and imbibition moisture-retaining capacity, fenestra are equal One property etc..With the popularization of lithium ion battery applications, the requirement to lithium ion battery separator is also higher and higher, however commercialized Polyethylene diagrams are not well positioned to meet the market demand, for example, mechanical strength, punctured resistance, heat resistance it is inadequate caused by pacify Full hidden danger.

In order to promote the security performance of lithium ion battery separator, it is set to meet the market demand, it has been tried to inorganic The addition of filler, the coating of heat-resisting material layer, multilayered structure the various methods such as diaphragm.Such as German Degussa (Degussa) company discloses a kind of preparation method of Separion ceramic diaphragm of Patent No. US20110206971A, i.e., Composite alumina or other inorganic matters on cellulose nonwoven cloth, Separion ceramic diaphragm embody that cellulose is heated to be not easy The characteristic of deformation, does not shrink and melting phenomenon at 200 DEG C, and the safety of power battery can be improved, still, the preparation The phase inversion that journey is related to is more complex, costly, and diaphragm combined strength bination inorganic coating is easy to fall off, to cause safety hidden Suffer from.

Summary of the invention

To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of one-dimensional nano line The preparation method of polymer-modified diaphragm.

Another object of the present invention is to improve a kind of polymer-modified diaphragm of one-dimensional nano line made from the above method.It should Diaphragm safety is good, punctured resistance and tensile strength are high, has preferable heat resistance, porosity and ionic conductivity.

A further object of the present invention is to provide a kind of above-mentioned applications of the polymer-modified diaphragm of one-dimensional nano line.

The object of the invention is achieved through the following technical solutions:

A kind of preparation method of the polymer-modified diaphragm of one-dimensional nano line, comprising the following steps:

(1) it disperses one-dimensional nano line in paraffin oil, silane coupling agent is then added, react 10 at 20~140 DEG C ~120min obtains silane coupler modified one-dimensional nano line dispersion liquid；

(2) by melting of polymer pellets at 220~240 DEG C, the silane coupler modified one-dimensional of step (1) is then added Nanowire dispersion reacts 10~120min, obtains the polymer-modified mixed liquor of one-dimensional nano line；

(3) the polymer-modified mixed liquor of one-dimensional nano line is filmed using wet process, it is modified poly- obtains one-dimensional nano line Close object diaphragm；

Wherein, step (2) polymer is polyethylene, polypropylene, polyethylene terephthalate (PET) and gathers inclined fluorine At least one of ethylene (PVDF)；

A silane coupler modified wiener in the polymer beads and silane coupler modified one-dimensional nano line dispersion liquid The mass ratio of rice noodles is 10:1~1:10.

Step (1) described one-dimensional nano line is preferably one-dimensional carbon nanotube, one-dimensional hydroxyapatite nano line, one-dimensional bumps One or more of stick nano wire, one-dimensional Kocide SD nano wire, one-dimensional silica white nano-wire and one-dimensional silver nanowires, The length of the one-dimensional nano line is preferably 50~3000nm, more preferably 1000~3000nm, and width is preferably 10~40nm, More preferably 15~40nm.

The mass ratio of step (1) one-dimensional nano line and paraffin oil is preferably (0.01~1): (0.01~1)；More preferably For 0.1:1.

The mode of step (1) described dispersion preferably stirs or ultrasonic vibration, and the speed of agitator is preferably 8000~ 10000r/min；The power of the ultrasonic vibration is preferably 400~500W；The jitter time is preferably 0.1~for 24 hours, it is more excellent It is selected as 0.1~4h；Temperature is preferably 20~140 DEG C, and more preferably 20~120 DEG C.

The mass ratio of step (1) silane coupling agent and one-dimensional nano line is preferably (0.0001~2): 1；More preferably (0.11~2): 1.

Step (1) described silane coupling agent is preferably one or more of KH550, KH560 and KH570.

Step (1) described reaction temperature is preferably 20~120 DEG C；Reaction time is preferably 10~60min.

Step (2) polymer beads with it is silane coupler modified in silane coupler modified one-dimensional nano line dispersion liquid The mass ratio of one-dimensional nano line is preferably 6~10:1.

Step (2) reaction time is preferably 10~20min.

Step (3) described wet process is thermally induced phase separation, and the wet process is this field common process method.

A kind of preparation method of the polymer-modified diaphragm of one-dimensional nano line, comprising the following steps:

(1) it disperses one-dimensional nano line in paraffin oil, silane coupling agent is then added, react 10 at 20~140 DEG C ~120min obtains silane coupler modified one-dimensional nano line dispersion liquid；Filtering, obtains silane coupler modified 1-dimention nano Line；

(2) by melting of polymer pellets at 220~240 DEG C, the silane coupler modified one-dimensional of step (1) is then added Nano wire reacts 10~120min, obtains the polymer-modified mixture of one-dimensional nano line；

(3) the polymer-modified mixture of one-dimensional nano line is filmed using dry method list daraf(reciprocal of farad), obtains one-dimensional nano line Polymer-modified diaphragm；

Wherein, the polymer is polyethylene, polypropylene, polyethylene terephthalate (PET) and Kynoar At least one of (PVDF)；

The mass ratio of the polymer beads and silane coupler modified one-dimensional nano line is 10:1~1:10.

Step (1) described one-dimensional nano line is preferably one-dimensional carbon nanotube, one-dimensional hydroxyapatite nano line, one-dimensional bumps One or more of stick nano wire, one-dimensional Kocide SD nano wire, one-dimensional silica white nano-wire and one-dimensional silver nanowires, The length of the one-dimensional nano line is preferably 50~3000nm, more preferably 1000~3000nm, and width is preferably 10~40nm, More preferably 15~40nm.

The mass ratio of step (1) one-dimensional nano line and paraffin oil is preferably (0.01~1): (0.01~1)；More preferably For 0.1:1.

The mode of step (1) described dispersion preferably stirs or ultrasonic vibration, and the speed of agitator is preferably 8000~ 10000r/min；The power of the ultrasonic vibration is preferably 400~500W；The jitter time is preferably 0.1~for 24 hours, it is more excellent It is selected as 0.1~4h；Temperature is preferably 20~140 DEG C, and more preferably 20~120 DEG C.

The mass ratio of step (1) silane coupling agent and one-dimensional nano line is preferably (0.0001~2): 1；More preferably (0.11~2): 1.

Step (1) described silane coupling agent is preferably one or more of KH550, KH560 and KH570.

Step (1) described reaction temperature is preferably 20~120 DEG C；Reaction time is preferably 10~60min.

The mass ratio of step (2) polymer beads and silane coupler modified one-dimensional nano line is preferably 5~10:1.

Step (2) reaction time is preferably 10~20min.

Step (3) the dry method list daraf(reciprocal of farad) is this field common process method.

A kind of polymer-modified diaphragm of one-dimensional nano line made from the above method.

In the molecular structure of the polymer-modified diaphragm of one-dimensional nano line containing a large amount of such as hydroxyls, phenolic hydroxyl group, carboxyl, The negatively charged active group such as amino, improves the hydrophily of membrane for polymer；The diaphragm is a kind of perforated membrane.

The thickness of the polymer-modified diaphragm of one-dimensional nano line is preferably 6~50 μm, and more preferably 6~20 μm, hole The percent by volume of rate is preferably 35~52%.

A kind of application of the above-mentioned polymer-modified diaphragm of one-dimensional nano line in field of lithium ion battery.

The application is preferably used as lithium battery diaphragm.

Compared with prior art, the present invention has the following advantages and beneficial effects:

(1) the polymer-modified diaphragm of one-dimensional nano line of the present invention, introduced in polyethylene diagrams a large amount of such as hydroxyls, The negatively charged active group such as phenolic hydroxyl group, carboxyl, amino, while improving the hydrophily of base film.

(2) in the polymer-modified diaphragm of one-dimensional nano line of the present invention, by quiet between one-dimensional nano line and polymer Electro ultrafiltration and Hydrogenbond, so that its binding force enhances, it is not easy to fall off in use process.

(3) in the obtained diaphragm of the present invention, the length of one-dimensional nano line is 500~3000nm, and width is 10~40nm, one-dimensional Bridge joint network structure is formed between nano wire and polymer, the fenestra of base film will not be blocked, to guarantee the hole of modified diaphragm Gap rate and ionic conductivity.

(4) one-dimensional nano line of the present invention has good mechanical strength, can greatly improve the puncture resistant of composite diaphragm Intensity and tensile strength, and also improve to the heat resistance of base film.

Specific embodiment

Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.

Wet process film technique described in the embodiment of the present application and dry method list daraf(reciprocal of farad) filming technology are according to this field routine work Skill parameter carries out；The porosity is calculated according to percent by volume；The test method of the ionic conductivity is that this field is conventional Method.