CN108832064A - A kind of composite ceramic porous lithium electric separator, preparation method and applications - Google Patents
A kind of composite ceramic porous lithium electric separator, preparation method and applications Download PDFInfo
- Publication number
- CN108832064A CN108832064A CN201810673343.2A CN201810673343A CN108832064A CN 108832064 A CN108832064 A CN 108832064A CN 201810673343 A CN201810673343 A CN 201810673343A CN 108832064 A CN108832064 A CN 108832064A
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- Prior art keywords
- lithium electric
- composite ceramic
- ceramic porous
- diaphragm
- electric separator
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
-
- 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
Abstract
The invention discloses a kind of composite ceramic porous lithium electric separators, preparation method and applications, it is with polyethylene 18~35%, pore creating material 50~60%, antioxidant 5~8%, ceramic particle 3~8% is raw material, membrane process is prepared by wet process, nanometer scale ceramics diaphragm is uniformly added into stock preparation process, as polyethylene raw material squeezes out together, it stretches, it is impregnated using organic solvent and removes pore creating material, form the diaphragm with porous structure, composite ceramic porous lithium electric separator is obtained after last setting process, the present invention is using wet process membrane process and the primary completion of ceramic particle blending, substantially reduce the processing cost of ceramic diaphragm, the high-temperature stability of lithium electric separator is improved simultaneously.
Description
Technical field
Even if the present invention relates to a kind of ceramic lithium electric separator fields.Specifically composite ceramic porous lithium electric separator, system
Preparation Method and its application.
Background technique
Since traditional ceramic lithium electric separator is that one or both sides in diaphragm matrix coat one layer and contain ceramic particle
Coating, the coating processes require it is stringenter because easily causing coating uneven or uneven in the figure layer of ceramic particle
Phenomenon, which is easy to cause lithium electric separator, and stability reduces at high temperature.Due to lithium battery be widely used in mobile phone, computer,
The fields such as electric car, the voltage and capacity that lithium battery is born constantly increase, have more to the high-temperature stability of lithium electric separator
High requirement, and traditional ceramics lithium electric separator, in hot operation, the ceramic particle of coating is extremely easy to drop, causes lithium battery positive and negative
Short circuit occurs for pole, to generate serious safety accident.Therefore, a simple process is urgently researched and developed at present and there is high-temperature stable
The lithium electric separator of property.
Summary of the invention
The purpose of the present invention is to provide a kind of composite ceramics lithium electric separator of high-temperature stability, preparation method and its answer
With.
Solution of the invention is to prepare membrane process by wet process, and nanoscale is uniformly added into stock preparation process
Then ceramic diaphragm removes diaphragm using abstraction technique as polyethylene raw material, pore creating material, antioxidant squeeze out together, stretches
In pore creating material, form composite ceramic porous lithium electric separator.
The present invention provides a kind of composite ceramic porous lithium electric separator, the raw material including following components by weight percent：
Polyethylene 18~35%, pore creating material 50~60%, antioxidant 5~8%, ceramic particle 3~8%, the above each group
Dividing the sum of mass fraction is 100%, and the ceramic particle partial size is 10~30nm.
Preferably, the aperture of composite ceramic porous lithium electric separator is 50~100nm.
Preferably, the molecular weight of the polyethylene is 1,000,000~1,500,000.
Preferably, the pore creating material is at least one of white oil, paraffin oil or kerosene.
Preferably, the antioxidant is 2,6- di-tert-butyl-4-methy phenol, pentaerythrite-four-[3- (3,5- bis- uncles
Butyl -4- hydroxy phenyl) acrylate], in octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyl) acrylate extremely
Few one kind.
The present invention also provides the preparation methods of the composite ceramic porous lithium electric separator, specifically include following steps：
(1) it weighs the raw material of the weight ratio and is sufficiently mixed；
(2) mixed raw material in step (1) is obtained into high-temperature fusant through the double screw extruder that excess temperature is 180 DEG C, it is high
Warm melt is sent into after Melt Pump is accurately measured gets to know, and the high-temperature fusant being sent into getting to know is flowed out from die slit mouth, from mould
The high-temperature fusant of head slit mouth outflow obtains squeezing out slab after sharp cooling roll is handled；
(3) squeezing out slab to enter bi-directional synchronization stretching-machine to obtain vertical Lapie is 4~4.5 times, and horizontal Lapie is 5~5.5 times
Oil-containing film；
(4) oil-containing diaphragm is subjected to 10~20min of immersion using organic solvent, sufficiently removes the pore creating material in diaphragm, then
By the drying and volatilizing organic solvent, microporous barrier is formed, drying temperature is 35~45 DEG C；
(5) micro-pore septum that step (4) obtains sufficiently removes diaphragm stress in 130 DEG C of high-temperature shaping device, finally
Diaphragm winds to obtain composite ceramic porous lithium electric separator through online winder, and aperture is 50~100nm.
Preferably, the organic solvent is at least one of methylene chloride, carbon tetrachloride or ether.
By application of the composite ceramic porous lithium electric separator prepared by the present invention in lithium battery.
Compared with prior art, advantageous effects of the invention：Using composite ceramic porous lithium electricity prepared by the present invention
The phenomenon that diaphragm effectively prevent the ceramic powders in diaphragm to fall reduces battery short circuit phenomenon, and during applied at elevated temperature
With preferable stability；The prior art is compared, the present invention, which uses, is processed and formed at one time technique, simple process, at low cost, molding
Rate is high, can be mass-produced, improves production efficiency.
Specific embodiment
Embodiment 1
(1) it weighs the raw material of following weight ratio and is sufficiently mixed：The polyethylene 30% that average molecular weight is 1,200,000, kerosene
55%, octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyl) acrylate 8%, partial size are the ceramic particle 7% of 10nm.
(2) raw material mixed is obtained into high-temperature fusant by 180 DEG C of double screw extruder, high-temperature fusant is through Melt Pump
It is sent into after accurate metering in getting to know, the high-temperature fusant being sent into getting to know is flowed out from die slit mouth, is flowed out from die slit mouth
High-temperature fusant obtains squeezing out slab after sharp cooling roll；
(3) squeezing out slab to enter bi-directional synchronization stretching-machine to obtain vertical Lapie is 4 times, the oil-containing film that horizontal Lapie is 5 times；
(4) after oil-containing diaphragm sufficiently being impregnated 15min using methylene chloride, the pore creating material in diaphragm is removed, then by dry
Dry volatilization organic solvent, forms microporous barrier, and drying temperature is 40 DEG C；
(5) micro-pore septum that step (4) obtains keeps the temperature 5h in 130 DEG C of high-temperature shaping device, sufficiently removes diaphragm and answers
Power, last diaphragm wind to obtain composite ceramic porous lithium electric separator through online winder.Through detecting, the composite ceramic porous lithium electricity
The aperture of diaphragm is 120nm.Measure the porosity and ventilative value of diaphragm material of the invention, and test its respectively 105 DEG C with
130 DEG C of heating, 1 hour post-shrinkage ratio, the results are shown in Table 1.
Table 1
Embodiment 2
According to the technique of embodiment 1, feed change and its proportion, other process conditions are constant, specific raw material and with such as
Under：The polyethylene 25% that average molecular weight is 1,300,000, paraffin oil 60%, pentaerythrite-four-[3- (3,5- di-t-butyl -4- hydroxyls
Base phenyl) acrylate] 8%, partial size is the ceramic particle 7% of 20nm.
Through detecting, the aperture of the composite ceramic porous lithium electric separator is 110nm.Measure the hole of diaphragm material of the invention
Rate and ventilative value, and it is tested respectively in 105 DEG C and 130 DEG C heating, 1 hour post-shrinkage ratio, the results are shown in Table 2.
Table 2
Embodiment 3
According to the technique of embodiment 1, feed change and its proportion, other process conditions are constant, specific raw material and with such as
Under：The polyethylene 25% that average molecular weight is 1,300,000, white oil 60%, 2,6- di-tert-butyl-4-methy phenol 8%, partial size are
The ceramic particle 7% of 30nm.
Through detecting, the aperture of the composite ceramic porous lithium electric separator is 130nm.Measure the hole of diaphragm material of the invention
Rate and ventilative value, and its shrinking percentage after heating 1 hour at 105 DEG C and 130 DEG C respectively is tested, the results are shown in Table 3.
Table 3
Embodiment 4
It is applied to the diaphragm material of Examples 1 to 3 preparation to be used as battery diaphragm in lithium battery respectively, with LiCoO2It is positive
Button cell C1~C3 is made using Li as negative electrode material in pole material.Battery is tested using following charging/discharging thereof：It adopts
Above-mentioned button cell C1~C3 is charged into 4.2V with 0.2mA crossing current with battery test cabinet, then constant-voltage charge to electric current is less than
0.1mA, then be discharged to 3V with 0.2mA, gained discharge capacity are the quality specific volume of button cell divided by the quality of positive electrode
Amount.
Measure button cell C1~C3 specific discharge capacity at room temperature.According to above-mentioned charging/discharging thereof, button type is electric at room temperature
Pond C1~C3 is tested, and the specific discharge capacity of button cell at room temperature is measured.
The specific discharge capacity of button cell C1~C3 at 85 DEG C of measurement.Button cell C1~C3 is stored at 85 DEG C respectively
1 hour, the specific discharge capacity of its button cell at 85 DEG C is measured using above-mentioned charging/discharging thereof.
The security performance of button cell C1~C3 at 140 DEG C of measurement.Button cell C1~C3 is heated 2 at 140 DEG C respectively
Hour, then tested using above-mentioned charging/discharging thereof, if button cell can normal charge and discharge, illustrate that oneself does not occur hides
Disconnected, there are security risks for battery；If button cell is unable to charge and discharge, illustrate to have occurred from interdicting, battery is very safe；If
There are part charge and discharge for button cell, then illustrate battery there are some potential safety problems, determination data is as shown in table 4.
Table 4
| Button cell | Specific discharge capacity at room temperature | Specific discharge capacity at 85 DEG C | Security performance at 140 DEG C |
| C1 | 143.5mAh/g | 127.7mAh/g | It is unable to charge and discharge |
| C2 | 142.4mAh/g | 125.3mAh/g | It is unable to charge and discharge |
| C3 | 1408Ah/ | 1224Ah/ | It is unable to charge and discharge |
Embodiment described above is only that preferred embodiment of the invention is described, and is not carried out to the scope of the present invention
It limits, under the basis for not departing from spirit of that invention, those of ordinary skill in the art can be done technical solution of the present invention
Various modifications and improvements out should all be fallen into the protection scope that claims of the present invention determines.
Claims (7)
1. a kind of composite ceramic porous lithium electric separator, which is characterized in that the raw material including following components by weight percent：
Polyethylene 18~35%,
Pore creating material 50~60%,
Antioxidant 5~8%,
Ceramic particle 3~8%,
The sum of the above components mass fraction is 100%,
The ceramic particle partial size is 10~30nm.
2. composite ceramic porous lithium electric separator according to claim 1, it is characterised in that：The hole of the porous lithium electric separator
50~100nm of diameter.
3. composite ceramic porous lithium electric separator according to claim 1, which is characterized in that the molecular weight of the polyethylene is
1000000~1,500,000.
4. composite ceramic porous lithium electric separator according to claim 1, which is characterized in that the pore creating material be white oil,
At least one of paraffin oil or kerosene；The antioxidant is 2,6 di tert butyl 4 methyl phenol, pentaerythrite-four-
[3- (3,5- di-tert-butyl-hydroxy phenyl) acrylate], octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyl) third
At least one of olefin(e) acid ester.
5. a kind of preparation method of composite ceramic porous lithium electric separator, which is characterized in that include the following steps：
(1) it weighs the raw material of the weight ratio and is sufficiently mixed；
(2) mixed raw material in step (1) is obtained into high-temperature fusant, high temperature melting through the double screw extruder that excess temperature is 180 DEG C
Body is sent into after Melt Pump is accurately measured gets to know, and the high-temperature fusant being sent into getting to know is flowed out from die slit mouth, narrow from die head
The high-temperature fusant of sealing outflow obtains squeezing out slab after sharp cooling roll；
(3) squeezing out slab to enter bi-directional synchronization stretching-machine to obtain vertical Lapie is 4~4.5 times, the oil-containing that horizontal Lapie is 5~5.5 times
Film；
(4) oil-containing diaphragm is subjected to 10~20min of immersion using organic solvent, sufficiently removes the pore creating material in diaphragm, then pass through
The drying and volatilizing organic solvent, forms microporous barrier, and drying temperature is 35~45 DEG C；
(5) micro-pore septum that step (4) obtains sufficiently removes diaphragm stress, last diaphragm in 130 DEG C of high-temperature shaping device
It winds to obtain composite ceramic porous lithium electric separator through online winder, aperture is 50~100nm.
6. the preparation method of composite ceramic porous diaphragm according to claim 5, which is characterized in that described in step (4)
Organic solvent is at least one of methylene chloride, carbon tetrachloride or ether.
7. application of described in any item composite ceramic porous lithium electric separators in lithium battery according to claim 1~6.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560235A (en) * | 2018-12-05 | 2019-04-02 | 河北金力新能源科技股份有限公司 | A kind of new type lithium ion battery aramid fiber diaphragm preparation method |
| CN110165129A (en) * | 2019-05-28 | 2019-08-23 | 大连中比动力电池有限公司 | Anti-oxidant high puncture strength dry method diaphragm of one kind and its preparation method and application |
| CN110165127A (en) * | 2019-06-24 | 2019-08-23 | 卓文晓 | A kind of modification lithium-ion battery diaphragm and preparation method thereof |
| CN113644379A (en) * | 2021-01-18 | 2021-11-12 | 华南理工大学 | Porous ceramic fiber diaphragm material for thermal battery and preparation method thereof |
| CN114464908A (en) * | 2022-04-13 | 2022-05-10 | 四川新能源汽车创新中心有限公司 | Three-dimensional porous coating for lithium ion battery and preparation and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109560235A (en) * | 2018-12-05 | 2019-04-02 | 河北金力新能源科技股份有限公司 | A kind of new type lithium ion battery aramid fiber diaphragm preparation method |
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| CN110165129A (en) * | 2019-05-28 | 2019-08-23 | 大连中比动力电池有限公司 | Anti-oxidant high puncture strength dry method diaphragm of one kind and its preparation method and application |
| CN110165127A (en) * | 2019-06-24 | 2019-08-23 | 卓文晓 | A kind of modification lithium-ion battery diaphragm and preparation method thereof |
| CN110165127B (en) * | 2019-06-24 | 2022-10-18 | 安徽今希新材料科技有限公司 | Modified lithium ion battery diaphragm and preparation method thereof |
| CN113644379A (en) * | 2021-01-18 | 2021-11-12 | 华南理工大学 | Porous ceramic fiber diaphragm material for thermal battery and preparation method thereof |
| CN114464908A (en) * | 2022-04-13 | 2022-05-10 | 四川新能源汽车创新中心有限公司 | Three-dimensional porous coating for lithium ion battery and preparation and application thereof |
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