CN103730618A - Alumina coated diaphragm and making method thereof - Google Patents
Alumina coated diaphragm and making method thereof Download PDFInfo
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- CN103730618A CN103730618A CN201210388888.1A CN201210388888A CN103730618A CN 103730618 A CN103730618 A CN 103730618A CN 201210388888 A CN201210388888 A CN 201210388888A CN 103730618 A CN103730618 A CN 103730618A
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- Prior art keywords
- barrier film
- coating alumina
- alumina
- diaphragm
- preparation
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an alumina coated diaphragm and a making method thereof. The method comprises the following steps: infiltrating a diaphragm subjected to hydrophilic treatment in a salt solution of Al<3+>, vertically pulling out, baking the obtained diaphragm in ammonia gas and nitrogen mixed atmosphere for 6min-24h, carrying out room temperature drying to obtain a diaphragm containing aluminum hydroxide, compacting, carrying out baking dehydration under a nitrogen or vacuum condition, cooling, sequentially washing with water and alcohol, and drying to obtain the alumina coated diaphragm. The method has the advantages of avoiding of the use of an organic matter or other additives, substantial shortening of the reaction time, no need of high temperature sintering, simplicity, effective improvement of the coating tightness and uniformity of alumina, and difficult dusting.
Description
Technical field
The invention belongs to material chemistry technical field, be specifically related to barrier film of a kind of coating alumina and preparation method thereof.
Background technology
Barrier film is as one of layer assembly in the key in lithium ion battery, and the key characteristics such as its capacity on battery, cycle performance, charging and discharging currents density have direct impact, and the barrier film of excellent performance plays an important role to the combination property that improves battery.Adopt aluminium oxide as coating material, be coated in lithium battery diaphragm surface can be when electric current be excessive, volumetric expansion, effectively blocks electric current, for high-power lithium battery high-energy spend in comfort and safe and reliable discharge and recharge provide may.And, there is very good heat conductivility and good anti-flammability, can stop large-scale burning even to be exploded, thereby improve the fail safe of battery.
In prior art, recorded some and used the barrier film preparation method that inorganic salts are raw material, but there is following shortcoming in these methods: first, need to add organic substance or other additives, complex process and not environmental protection; Secondly, the reaction time is longer, often needs several days or a few week; The 3rd, reaction condition is had relatively high expectations, conventionally need high temperature.The Degussa of Germany is directly pressed onto diaphragms by inorganic particle by the form of hot pressing, easily occurs dry linting phenomenon, causes that barrier film character changes, thereby directly affects lithium battery capacity and charge-discharge performance.
Summary of the invention
For addressing the above problem, the present invention aims to provide a kind of barrier film preparation method of coating alumina, the method has been avoided the use of organic substance or other additives, and greatly shortened the reaction time, do not need high temperature sintering, technique is simple, can also effectively improve compactness and the uniformity of alumina coated, and be difficult for dry linting.
The barrier film preparation method of a kind of coating alumina provided by the invention, is characterized in that, comprises the following steps: the barrier film through hydrophilic treated is infiltrated at Al
3+salting liquid in, then vertically pull-out, under the atmosphere of ammonia and nitrogen mixture, toast 6 minutes ~ 24 hours, then carry out drying at room temperature, obtain the barrier film of aluminium hydroxide, compacting, under nitrogen or vacuum condition, carry out afterwards baking dehydration, cooling, then water, alcohol washing successively, final drying, obtains the barrier film of coating alumina.
Preferably, hydrophilic treated, for barrier film is immersed in dodecyl sodium sulfonate, polyethylene glycol or fluorine carbon alkane activating agent, is soaked 10 ~ 30 minutes, or barrier film is put into plasma processing chambers, pass into argon gas, open radio-frequency power supply, tune is established power to 500W, processes 0.5 ~ 10 minute under normal pressure.
Preferably, barrier film is the one in polypropylene (PP) barrier film, polypropylene, polyethylene/polypropylene (PP/PE/PP) barrier film, PETG (PET) nonwoven fabrics barrier film.
Preferably, Al
3+salting liquid be Al
2(SO
4)
3, Al (NO
3)
3or AlCl
3solution.
Preferably, Al
3+the concentration of salting liquid be 1mol/L.
Preferably, in the atmosphere of ammonia and nitrogen mixture, the volume ratio of ammonia and nitrogen is 1:1 ~ 10.
Preferably, in the atmosphere of ammonia and nitrogen mixture, 80 ~ 120 ° of C toast 6 minutes ~ 24 hours.
Preferably, be compressed to by twin rollers and carry out pair roller, 2 × 10
5under Pa pressure, suppress.
Preferably, the time of baking dehydration is 1 ~ 24 hour, and temperature is 150 degree.
Preferably, the average particulate diameter of aluminium oxide is 0.05 ~ 1 μ m;
The present invention also provides the barrier film of the coating alumina that said method makes.
In prior art, often with adhesive, active material is bonded on battery diaphragm, but in battery charge and discharge process, may causes that adhesive, by phenomenons such as electrolyte are swelling, break, causes battery short circuit to set off an explosion, therefore have certain potential safety hazard.Compared with prior art, the present invention has avoided the use of organic substance or other additives, directly by alumina coated and membrane surface, reduces unnecessary internal resistance in battery, guarantee the UNICOM between the interfaces such as in battery charging and discharging circulation active material, collector, improved the performance of barrier film.And the reaction time of the present invention is short, do not need high temperature sintering, technique is simple, can effectively improve compactness and the uniformity of alumina coated, and be difficult for dry linting.By adding aluminium oxide nano coating, improve the thermal endurance of battery diaphragm, the fail safe that improves battery.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the barrier film electron microscope picture of the aluminum oxide coating layer of the embodiment of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, 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.
PP barrier film is immersed in dodecyl sodium sulfonate to 10 minutes, makes it surface hydrophilic, take out, then the barrier film of this processing is immersed in to the Al of 1mol/L
2(SO
4)
3in solution, vertically pull-out, under the atmosphere of ammonia and nitrogen mixture (volume ratio 1:1), 80 ° of C toast 6 minutes, then carry out drying at room temperature, obtain the barrier film of aluminium hydroxide, carry out pair roller, 2 × 10 by twin rollers
5under Pa pressure, suppress, then under condition of nitrogen gas, carry out 150 degree baking dehydration 1 hour, then at room temperature cooling, then water, alcohol washing successively, final drying, obtains the barrier film containing γ – aluminium oxide thin layer.
As shown in Figure 1, in barrier film, the average particulate diameter of aluminium oxide is 0.1 μ m to the electron microscope picture of the barrier film of gained coating alumina as seen from the figure.
Embodiment 2
PP/PE/PP barrier film is put into plasma processing chambers, pass into argon gas, open radio-frequency power supply, adjust and establish power to 500W, under normal pressure, process 10 minutes, make it surface hydrophilic, take out, then the barrier film of this processing is immersed in to the Al (NO of 1mol/L
3)
3in solution, vertically pull-out, under the atmosphere of ammonia and nitrogen mixture (volume ratio 1:3), 100 ° of C toast 24 hours, then carry out drying at room temperature, obtain the barrier film of aluminium hydroxide, carry out pair roller, 2 × 10 by twin rollers
5under Pa pressure, suppress, then under vacuum condition, carry out 150 degree baking dehydration 24 hours, then at room temperature cooling, then water, alcohol washing successively, final drying, obtains the barrier film containing gama-alumina thin layer, and in barrier film, the average particulate diameter of aluminium oxide is 1 μ m.
Embodiment 3
PP barrier film is immersed in polyethylene glycol to 20 minutes, makes it surface hydrophilic, take out, then the barrier film of this processing is immersed in to the AlCl of 1mol/L
3in solution, vertically pull-out, under the atmosphere of ammonia and nitrogen mixture (volume ratio 1:5), 120 ° of C toast 2 hours, then carry out drying at room temperature, obtain the barrier film of aluminium hydroxide, carry out pair roller, 2 × 10 by twin rollers
5under Pa pressure, suppress, then under condition of nitrogen gas, carry out 150 degree baking dehydration 12 hours, then at room temperature cooling, by twin rollers, carry out pair roller, 2 × 10
5under Pa pressure, suppress, then water, alcohol washing successively, final drying, obtains the barrier film containing γ – aluminium oxide thin layer, and in barrier film, the average particulate diameter of aluminium oxide is 0.05 μ m.
Embodiment 4
PET nonwoven fabrics barrier film is immersed in fluorine carbon alkane activating agent to 30 minutes, makes it surface hydrophilic, take out, then the barrier film of this processing is immersed in to the Al of 1mol/L
2(SO
4)
3in solution, vertically pull-out, under the atmosphere of ammonia and nitrogen mixture (volume ratio 1:10), 120 ° of C toast 2 hours, then carry out drying at room temperature, obtain the barrier film of aluminium hydroxide, carry out pair roller, 2 × 10 by twin rollers
5under Pa pressure, suppress, then under vacuum condition, carry out 150 degree baking dehydration 12 hours, then at room temperature cooling, by twin rollers, carry out pair roller, 2 × 10
5under Pa pressure, suppress, then water, alcohol washing successively, final drying, obtains the barrier film containing gamma-alumina thin layer, and in barrier film, the average particulate diameter of aluminium oxide is 0.6 μ m.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a barrier film preparation method for coating alumina, is characterized in that, comprises the following steps: the barrier film through hydrophilic treated is infiltrated at Al
3+salting liquid in, then vertically pull-out, under the atmosphere of ammonia and nitrogen mixture, toast 6 minutes ~ 24 hours, then carry out drying at room temperature, obtain the barrier film of aluminium hydroxide, compacting, under nitrogen or vacuum condition, carry out afterwards baking dehydration, cooling, then water, alcohol washing successively, final drying, obtains the barrier film of coating alumina.
2. the barrier film preparation method of coating alumina as claimed in claim 1, it is characterized in that, described hydrophilic treated is for to be immersed in barrier film in dodecyl sodium sulfonate, polyethylene glycol or fluorine carbon alkane activating agent, soak 10 ~ 30 minutes, or barrier film is put into plasma processing chambers, pass into argon gas, open radio-frequency power supply, tune is established power to 500W, processes 0.5 ~ 10 minute under normal pressure.
3. the barrier film preparation method of coating alumina as claimed in claim 1 or 2, is characterized in that, described barrier film is polypropylene diaphragm, polypropylene, polyethylene/polypropylene diaphragm, the one in PETG nonwoven fabrics barrier film.
4. the barrier film preparation method of coating alumina as claimed in claim 1, is characterized in that, described Al
3+salting liquid be Al
2(SO
4)
3, Al (NO
3)
3or AlCl
3solution.
5. the barrier film preparation method of coating alumina as claimed in claim 1, is characterized in that, described Al
3+the concentration of salting liquid be 1mol/L.
6. the barrier film preparation method of coating alumina as claimed in claim 1, is characterized in that, in the atmosphere of described ammonia and nitrogen mixture, the volume ratio of ammonia and nitrogen is 1:1 ~ 10.
7. the barrier film preparation method of coating alumina as claimed in claim 1, is characterized in that, described in be compressed to by twin rollers and carry out pair roller, 2 × 10
5under Pa pressure, suppress.
8. the barrier film preparation method of coating alumina as claimed in claim 1, is characterized in that, the described baking dehydration time is 1 ~ 24 hour, and temperature is 150 degree.
9. the barrier film preparation method of coating alumina as claimed in claim 1, is characterized in that, in the barrier film of described coating alumina, the average particulate diameter of aluminium oxide is 0.05 ~ 1 μ m.
10. a barrier film for coating alumina, is characterized in that: the barrier film of described coating alumina is by the method preparation described in 1 ~ 9 arbitrary claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210388888.1A CN103730618A (en) | 2012-10-15 | 2012-10-15 | Alumina coated diaphragm and making method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210388888.1A CN103730618A (en) | 2012-10-15 | 2012-10-15 | Alumina coated diaphragm and making method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN103730618A true CN103730618A (en) | 2014-04-16 |
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ID=50454613
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210388888.1A Pending CN103730618A (en) | 2012-10-15 | 2012-10-15 | Alumina coated diaphragm and making method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107851762A (en) * | 2015-07-10 | 2018-03-27 | 株式会社Lg化学 | Dividing plate and the electrochemical appliance including the dividing plate |
| CN110783516A (en) * | 2019-11-15 | 2020-02-11 | 吉林大学 | Lithium ion battery diaphragm, lithium ion battery and preparation method thereof |
-
2012
- 2012-10-15 CN CN201210388888.1A patent/CN103730618A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107851762A (en) * | 2015-07-10 | 2018-03-27 | 株式会社Lg化学 | Dividing plate and the electrochemical appliance including the dividing plate |
| CN110783516A (en) * | 2019-11-15 | 2020-02-11 | 吉林大学 | Lithium ion battery diaphragm, lithium ion battery and preparation method thereof |
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Application publication date: 20140416 |