CN103066228A - Preparation method for inorganic / organic multilayer composite separator - Google Patents
Preparation method for inorganic / organic multilayer composite separator Download PDFInfo
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- CN103066228A CN103066228A CN2012105777718A CN201210577771A CN103066228A CN 103066228 A CN103066228 A CN 103066228A CN 2012105777718 A CN2012105777718 A CN 2012105777718A CN 201210577771 A CN201210577771 A CN 201210577771A CN 103066228 A CN103066228 A CN 103066228A
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Abstract
The invention discloses a preparation method for an inorganic / organic multilayer composite separator. The method comprises: soaking a separator in an organic solvent, cleaning surface of the separator by using ultrasonic vibration for 15 ~ 30min, drying in an oven, and then cutting the separator into a square separator; placing the above square separator and a target material into a RF (radio frequency) sputtering device; adjusting the air pressure of the RF sputtering device to be 0.1 ~ 1.0Pa, and then feeding in reactant gas, the sputtering power being 5 ~ 80W and the sputtering time being 5 ~ 100min; running the device, so target material plasma bombards gas molecules to form inorganic matter / organic matter which deposit on both sides of the separator to obtain an inorganic / organic multilayer composite separator. By uniformly sputtering one layer or a plurality of layers of inorganic matter / organic matter on the porous separator surface, the dimensional stability of ordinary separators is effectively improved, and the heat resistance of the separator is improved.
Description
Technical field
The invention belongs to high-performance barrier film preparing technical field, be specifically related to a kind of inorganic/preparation method of organic multilayer composite diaphragm.
Background technology
Barrier film is subject to researcher's extensive concern as the important component part of lithium ion battery, and the high performance of lithium ion battery and the character of barrier film are closely bound up, and particularly in the lithium battery of large multiplying power, fast charging and discharging, the performance requirement of barrier film is more obvious.In view of barrier film has vital impact to the performance of actual battery, it must possess good chemistry, electrochemical stability and in the repeated charge process electrolyte be kept the height wettability, and the interface compatibility between barrier material and the electrode, barrier film all have considerable influence to the charge-discharge performance of lithium ion battery, cycle performance etc. to electrolytical retentivity.In addition, along with the fast development of power vehicle, to the fail safe of lithium-ion-power cell, particularly thermal endurance is had higher requirement, and one of key factor that affects security of lithium-ion-power cell is exactly the fail safe of barrier film.
The polypropylene (PP) that current widely used diaphragm material is TPO, polyethylene (PE), the thermal endurance of itself is all lower.Early stage work is that employing is compound so that the barrier film high security to be provided with polypropylene (PP) microporous barrier and polyethylene (PE) microporous barrier, carry out behind the microporous barrier compoundly as polypropylene and polyethylene are made respectively, redraw the preparation composite micro porous film after PP and PE hard elastics film is compound.Though these class methods can improve the fail safe of battery diaphragm to a certain extent, can't improve generally the thermal endurance of barrier film.
Recently, for solving the problem of battery diaphragm fail safe, the researcher proposes MULTILAYER COMPOSITE, and organic/organic barrier film or inorganic/organic barrier film solve the problem of high temperature lower diaphragm plate fail safe.The method that proposes to adopt the polymer/metal oxide ceramic powder to apply such as patent CN 102683629 A prepares multilayer complex films, patent CN102569700A mentions being scattered in the polymer after ceramic powders is surface-functionalized again and prepares multilayer complex films in the polyalkene diaphragm surface-coated, patent CN 101989651 A mention and adopt crosslinked method to prepare the MULTILAYER COMPOSITE barrier film, the heat resisting temperature of these barrier films all can reach 150 ℃, but thickness has improved the thickness of barrier film greatly at 5-20 μ m.Some researchers consider to use the method for ion sputtering to prepare multilayer complex films, such as patent CN 102427119A, CN 102709592A mentions and adopts the method for ion sputtering to plate inorganic layer at membrane surface, can improve thermal endurance, thickness also can effectively be controlled, but coating is subject to the restriction of target, particularly high-purity target of nitride, oxide is expensive, the preparation difficulty is large, and is larger to the restriction of barrier film functionalization, is difficult to promote the use of.
At present, widely used painting method exists thickness to be difficult to control, the problem that exists powder to disperse inhomogeneous, conglomeration, caking in the slurry, and the poor storage stability of slurry simultaneously significantly precipitation and the problem that is difficult to twice dispersing occur after leaving standstill a period of time.Though and the new ion sputtering method that proposes can effectively be controlled thickness, is subject to the restriction of target, particularly the difficulty in the preparation of special target brings obstruction for the preparation of the controlled high performance barrier film of thickness.
Summary of the invention
The object of the present invention is to provide a kind of inorganic/preparation method of organic multilayer composite diaphragm, the invention provides a kind ofly in all kinds of atmosphere atmosphere, utilize simple target to adopt the preparation of reaction RF sputtering method to have the septum for lithium ion battery of functionalization coating.This type of membrane surface is smooth, and the overlay coating selectivity is high, the barrier film excellent heat resistance, and thickness is controlled.Particularly under 150 ℃, through 1 hour heat treatment, shrinking did not appear in barrier film substantially.
Provided by the invention a kind of inorganic/preparation method of organic multilayer composite diaphragm, comprise the steps:
1) barrier film is immersed in the organic solvent, ultrasonic oscillation 15～30min cleaning membrane surface, dry in baking oven, then it is cut to square barrier film;
2) above-mentioned square barrier film and target are put into radio-frequency (RF) sputtering equipment;
3) air pressure of adjusting radio-frequency (RF) sputtering equipment is 0.1 ~ 1.0Pa, after be filled with reacting gas, sputtering power is that 5～80W, sputtering time are 5 ~ 100min;
4) operational outfit forms inorganic matter/organic deposition in the both sides of barrier film behind the target plasma bombardment gas molecule, makes inorganic/organic multilayer composite diaphragm.
In the step 1), described barrier film is a kind of in polyethylene barrier film, polypropylene diaphragm, polypropylene, polyethylene/polypropylene multi-layer composite diaphragm, the polypropylene non-woven fabric.
In the step 1), described organic solvent is one or more in acetone, absolute ethyl alcohol, methyl alcohol, the n-hexane.；
Step 2) in, described target is metal targets, nonmetal target or their mixture target; Described metal targets is nickel target, aluminium target, cobalt target, zirconium target or zinc target; Nonmetal target is silicon target; The mixture target is the sial target.
In the step 3), the air pressure of described radio-frequency (RF) sputtering equipment is 0.7Pa, and sputtering power is 15w, and sputtering time is 30min.
In the step 3), described reacting gas is one or both in high purity oxygen gas, the nitrogen.
The invention has the beneficial effects as follows:
Method by radio frequency sputtering is at one or more layers inorganic layer/organic layer of surface sputtering of Polyolefin Plastics barrier film, can the Effective Regulation thickness of coating by time control, surface uniform, Stability Analysis of Structures layering do not occur and comes off medium-term and long-term use of electrolyte, behind surface sputtering inorganic layer/organic layer, the close electrolyte property of barrier film be improved significantly, can effectively improve simultaneously the thermal endurance of barrier film, 160 ℃ of lower long-term uses, obvious contraction not occur.Select simultaneously the reaction radio frequency sputtering, wide to the selection of coating, can prepare the barrier film of multiple different coating by selecting different gas, can effectively reduce cost, promote cost performance.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is ESEM (SEM) figure of original barrier film.
Fig. 2 is the pattern scanning electron microscope (SEM) photograph of the composite diaphragm that makes of the method in the embodiment of the invention 5.
Through the SEM figure of reactive sputtering metacneme, contrast can be found out through reactive sputtering at the inorganic coating of membrane surface formation one deck.
Fig. 3 is the aluminium element distribution map of the composite diaphragm that makes of the method among the embodiment 5.
Wherein bright spot represents aluminium element, and as can be seen from the figure aluminium element is evenly distributed on membrane surface.
Fig. 4 is the interface scanning Electronic Speculum figure of the composite diaphragm that makes of the method among the embodiment 5.
The Cross Section Morphology of sputter metacneme has the obvious inorganic coating of one deck in the outside of organic film, contact closely with matrix, lamination do not occur, illustrates between sputter metacneme coating and matrix to be connected closely.Through what measure, the average thickness of sputtering layer is at 0.95 μ m.
Fig. 5 is the composite diaphragm that makes of the method among the embodiment 5 and the percent thermal shrinkage of basement membrane.
This figure has provided the percent thermal shrinkage test result of composite diaphragm and basement membrane, obvious shrinkage phenomenon appears in basement membrane after 150 ℃ as can be seen from Fig., composite diaphragm still can keep higher dimensional stability under 150 ℃, shrinkage is lower than 5%, can find out through reactive sputtering to have formed useful thermal insulation layer at membrane surface that the fail safe that improves barrier film is had great help.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Now take specifically according to the preparation method of organic/inorganic composite diaphragm and by the composite diaphragm of the method preparation as example, the present invention is further elaborated.
The polyethylene barrier film is immersed in the n-hexane, behind the ultrasonic oscillation 15min, in 80 ℃ baking oven, dries, barrier film after cleaning is cut into the square barrier film of 45cm * 50cm, puts it in the plated film chamber of radio-frequency (RF) sputtering equipment, select the nickel target as target, first plated film chamber air pressure is evacuated to 0.1Pa, after be filled with high pure nitrogen, sputtering power is elected 5W as, sputtering time is 5min, behind the arrestment, take out barrier film, repeat the top process after the upset, namely make the laminated diaphragm of two-sided composite nitride nickel.The result is better.
Embodiment 2
Polypropylene diaphragm is immersed in the acetone, behind the ultrasonic oscillation 15min, in 80 ℃ baking oven, dries, barrier film after cleaning is cut into the square barrier film of 50cm * 50cm, put it in the plated film chamber of radio-frequency (RF) sputtering equipment, the aluminium target is evacuated to 1Pa with plated film chamber air pressure first as target, after be filled with high purity oxygen gas, sputtering power is elected 80W as, and sputtering time is 100min, behind the arrestment, take out barrier film, repeat the laminated diaphragm that the top process namely makes two-sided composite alumina after the upset.The result is better.
Embodiment 3
Polypropylene, polyethylene/polypropylene multi-layer composite diaphragm is immersed in the methyl alcohol, behind the ultrasonic oscillation 20min, in 80 ℃ baking oven, dry, barrier film after cleaning is cut into the square barrier film of 70cm * 40cm, put it in the plated film chamber of radio-frequency (RF) sputtering equipment, select the cobalt target as target, first plated film chamber air pressure is evacuated to 0.4Pa, after be filled with high purity oxygen gas, sputtering power is elected 40W as, and sputtering time is 70min, behind the arrestment, take out barrier film, repeat the laminated diaphragm that the top process namely makes two-sided combined oxidation cobalt after the upset.The result is better.
Embodiment 4
Polypropylene non-woven fabric is immersed in the methyl alcohol, behind the ultrasonic oscillation 20min, in 80 ℃ baking oven, dries, barrier film after cleaning is cut into the square barrier film of 65cm * 55cm, put it in the plated film chamber of radio-frequency (RF) sputtering equipment, select silicon target as target, first plated film chamber air pressure is evacuated to 0.9Pa, after be filled with high pure nitrogen, sputtering power is elected 60W as, and sputtering time is 30min, behind the arrestment, take out barrier film, repeat the laminated diaphragm that the top process namely makes two-sided composite silicon nitride after the upset.The result is better.
Polypropylene diaphragm is immersed in the absolute ethyl alcohol, behind the ultrasonic oscillation 20min, in 80 ℃ baking oven, dries, barrier film after cleaning is cut into the square barrier film of 50cm * 55cm, put it in the plated film chamber of radio-frequency (RF) sputtering equipment, the aluminium target is evacuated to 0.7Pa with plated film chamber air pressure first as target, after be filled with high purity oxygen gas, sputtering power is elected 15W as, and sputtering time is 30min, behind the arrestment, take out barrier film, repeat the laminated diaphragm that the top process namely makes two-sided composite alumina after the upset.The result is best.
Embodiment 6
Polypropylene diaphragm is immersed in the methyl alcohol, behind the ultrasonic oscillation 5min, in 80 ℃ baking oven, dries, barrier film after cleaning is cut into the square barrier film of 70cm * 55cm, put it in the plated film chamber of radio-frequency (RF) sputtering equipment, select the zirconium target as target, first plated film chamber air pressure is evacuated to 0.3Pa, after be filled with high purity oxygen gas, sputtering power is elected 60W as, and sputtering time is 80min, behind the arrestment, take out barrier film, repeat the laminated diaphragm that the top process namely makes two-sided compound zirconia after the upset.The result is better.
Embodiment 7
The polyethylene barrier film is immersed in the absolute ethyl alcohol, behind the ultrasonic oscillation 5min, in 80 ℃ baking oven, dries, barrier film after cleaning is cut into the square barrier film of 40cm * 55cm, put it in the plated film chamber of radio-frequency (RF) sputtering equipment, select the zinc target as target, first plated film chamber air pressure is evacuated to 0.3Pa, after be filled with high pure nitrogen, sputtering power is elected 20W as, and sputtering time is 30min, behind the arrestment, take out barrier film, repeat the laminated diaphragm that the top process namely makes two-sided composite nitride zinc after the upset.The result is better.
Embodiment 8
Polypropylene non-woven fabric is immersed in the absolute ethyl alcohol, behind the ultrasonic oscillation 10min, in 80 ℃ baking oven, dry, barrier film after cleaning is cut into the square barrier film of 45cm * 55cm, put it in the plated film chamber of radio-frequency (RF) sputtering equipment, select the sial target as target, first plated film chamber air pressure is evacuated to 0.6Pa, after be filled with high purity oxygen gas, sputtering power is elected 15W as, and sputtering time is 30min, behind the arrestment, take out barrier film, repeat the laminated diaphragm that the top process namely makes two-sided composite alumina and silica after the upset.The result is better.
Claims (6)
1. the preparation method of inorganic/organic multilayer composite diaphragm is characterized in that comprising the steps:
1) barrier film is immersed in the organic solvent, ultrasonic oscillation 15～30min cleaning membrane surface, dry in baking oven, then it is cut to square barrier film;
2) above-mentioned square barrier film and target are put into radio-frequency (RF) sputtering equipment;
3) air pressure of adjusting radio-frequency (RF) sputtering equipment is 0.1 ~ 1.0Pa, after be filled with reacting gas, sputtering power is that 5～80W, sputtering time are 5 ~ 100min;
4) operational outfit forms inorganic matter/organic deposition in the both sides of barrier film behind the target plasma bombardment gas molecule, makes inorganic/organic multilayer composite diaphragm.
2. preparation method as claimed in claim 1 is characterized in that: in the step 1), described barrier film is a kind of in polyethylene barrier film, polypropylene diaphragm, polypropylene, polyethylene/polypropylene multi-layer composite diaphragm, the polypropylene non-woven fabric.
3. preparation method as claimed in claim 1, it is characterized in that: in the step 1), described organic solvent is one or more in acetone, absolute ethyl alcohol, methyl alcohol, the n-hexane.
4. preparation method as claimed in claim 1 is characterized in that: step 2) in, described target is metal targets, nonmetal target or their mixture target; Described metal targets is nickel target, aluminium target, cobalt target, zirconium target or zinc target; Nonmetal target is silicon target; The mixture target is the sial target.
5. preparation method as claimed in claim 1, it is characterized in that: in the step 3), the air pressure of described radio-frequency (RF) sputtering equipment is 0.7Pa, and sputtering power is 15w, and sputtering time is 30min.
6. preparation method as claimed in claim 1, it is characterized in that: in the step 3), described reacting gas is one or both in high purity oxygen gas, the nitrogen.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299195A (en) * | 2015-06-01 | 2017-01-04 | 龙能科技（苏州）有限公司 | The preparation method of barrier film and lithium ion battery |
| CN106654118A (en) * | 2016-11-09 | 2017-05-10 | 江南大学 | Lithium-ion battery composite membrane with thermal shutdown function and preparation method |
| CN107403896A (en) * | 2016-08-04 | 2017-11-28 | 深圳市烯谷能源控股有限公司 | A kind of method for preparing ceramic membrane with non-woven fabrics membrane surface in lithium battery |
| CN107475678A (en) * | 2016-08-04 | 2017-12-15 | 深圳市烯谷能源控股有限公司 | A kind of method for preparing ceramic membrane in PE membrane surfaces |
| CN110299498A (en) * | 2019-07-12 | 2019-10-01 | 上海飞顿新材料科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN112920651A (en) * | 2021-02-01 | 2021-06-08 | 廊坊艾格玛新立材料科技有限公司 | Fiber composite type fireproof corrosion-resistant powder coating and preparation method thereof |
| CN115020910A (en) * | 2022-07-25 | 2022-09-06 | 湖北亿纬动力有限公司 | Polyolefin diaphragm and preparation method and application thereof |
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| CN101903560A (en) * | 2007-12-21 | 2010-12-01 | 无穷动力解决方案股份有限公司 | Method for sputter targets for electrolyte films |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299195A (en) * | 2015-06-01 | 2017-01-04 | 龙能科技（苏州）有限公司 | The preparation method of barrier film and lithium ion battery |
| CN106299195B (en) * | 2015-06-01 | 2020-02-07 | 龙能科技（苏州）有限公司 | Preparation method of diaphragm and lithium ion battery |
| CN107403896A (en) * | 2016-08-04 | 2017-11-28 | 深圳市烯谷能源控股有限公司 | A kind of method for preparing ceramic membrane with non-woven fabrics membrane surface in lithium battery |
| CN107475678A (en) * | 2016-08-04 | 2017-12-15 | 深圳市烯谷能源控股有限公司 | A kind of method for preparing ceramic membrane in PE membrane surfaces |
| CN107475678B (en) * | 2016-08-04 | 2019-12-06 | 惠州市烯谷新能源产业技术研究院有限公司 | method for preparing ceramic membrane on surface of PE (polyethylene) diaphragm |
| CN106654118A (en) * | 2016-11-09 | 2017-05-10 | 江南大学 | Lithium-ion battery composite membrane with thermal shutdown function and preparation method |
| CN110299498A (en) * | 2019-07-12 | 2019-10-01 | 上海飞顿新材料科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN112920651A (en) * | 2021-02-01 | 2021-06-08 | 廊坊艾格玛新立材料科技有限公司 | Fiber composite type fireproof corrosion-resistant powder coating and preparation method thereof |
| CN115020910A (en) * | 2022-07-25 | 2022-09-06 | 湖北亿纬动力有限公司 | Polyolefin diaphragm and preparation method and application thereof |
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Application publication date: 20130424 |