CN108807790A - A kind of preparation method of the ceramic modified polyolefin porous membrane of dynamic lithium battery - Google Patents
A kind of preparation method of the ceramic modified polyolefin porous membrane of dynamic lithium battery Download PDFInfo
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- CN108807790A CN108807790A CN201810585730.0A CN201810585730A CN108807790A CN 108807790 A CN108807790 A CN 108807790A CN 201810585730 A CN201810585730 A CN 201810585730A CN 108807790 A CN108807790 A CN 108807790A
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- modified polyolefin
- polyolefin porous
- porous membrane
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- lithium battery
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M50/411—Organic material
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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
- H01M50/431—Inorganic material
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- 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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Abstract
The invention discloses a kind of dynamic lithium battery preparation methods of ceramic modified polyolefin porous membrane, include the following steps：1, barium sulfate powder and (C2H2F2) n are separately added into C5H9NO, form the mixed liquor of a concentration of 5.6-6.3% of barium sulfate, a concentration of 2.4-2.7% of (C2H2F2) n, dispersant is added in mixed liquor, mixed liquor is stirred using magnetic stirring apparatus；2, magnetic agitation forms centrotheca after 2 hours, and centrotheca is carried out ball milling 2 hours, obtains coating slurry；3, polypropylene matrix impregnated in ethanol and is ultrasonically treated, dried；4, coating slurry is coated uniformly on to the two sides of polypropylene matrix using dip-coating method；5, it dries at room temperature, is finally dried in vacuo 24 hours under the conditions of 60 DEG C, obtains ceramic modified polyolefin porous membrane.Using ceramic modified polyolefin porous membrane prepared by preparation method of the present invention, with electrolyte retention is high, thermal dimensional stability is good, porosity is high, conductivity is high.The battery performance and security performance of power aluminum cell can be effectively improved.
Description
Technical field
The present invention relates to dynamic lithium battery technical fields, and in particular to a kind of dynamic lithium battery is more with ceramic modified polyolefin
The preparation method of pore membrane.
Background technology
With the development that new-energy automobile is at full speed, lithium ion battery is widely used in automobile industry, thing followed peace
Full problem is also commonplace.The basic reason for causing power lithium-ion battery safety accident is that thermal runaway, thermal runaway occur for battery
Refer to that the destructiveness accident such as spontaneous combustion, explosion occurs for battery caused by thermal response between battery material.Diaphragm is and power lithium battery
The closely related component of pond security performance, is directly related to the security performance of power lithium-ion battery.
It is at present the diaphragm being most widely used in dynamic lithium battery by Ceramic Composite diaphragm prepared by matrix of polyolefin
Material, since there is ceramic coating excellent thermal stability, the thermal dimensional stability of composite diaphragm to be obviously improved.Meanwhile ceramics
Coating surface contains hydroxyl, and specific surface area is huge, can obviously improve wetting property of the electrolyte to diaphragm, the hole in ceramic coating
Gap structure can additionally possess a part of electrolyte, and the imbibition rate of composite diaphragm is obviously improved.
Existing ceramic diaphragm mostly uses the nano-scale alumina of high-purity, SiO2 etc., and cost of material is high.Power lithium is drawn high
The cost of battery.Therefore, a kind of ceramic modified polyene of dynamic lithium battery at low cost, can ensureing ceramic diaphragm performance is studied
Hydrocarbon perforated membrane has highly important research significance.
Invention content
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of dynamic lithium battery is with ceramic modified poly-
The preparation method of alkene perforated membrane, includes the following steps：1, barium sulfate powder and (C2H2F2) n are separately added into C5H9NO,
The mixed liquor of a concentration of 5.6-6.3% of barium sulfate, a concentration of 2.4-2.7% of (C2H2F2) n are formed, dispersion is added in mixed liquor
Agent is stirred mixed liquor using magnetic stirring apparatus；2, magnetic agitation forms centrotheca after 2 hours, and centrotheca is carried out ball milling 2
Hour, obtain coating slurry；3, polypropylene matrix impregnated in ethanol and is ultrasonically treated, dried；4, by coating slurry
The two sides of polypropylene matrix is coated uniformly on using dip-coating method；5, it dries at room temperature, finally vacuum is dry under the conditions of 60 DEG C
Dry 24 hours, obtain ceramic modified polyolefin porous membrane.
The weight of dispersant is the 2% of blanc fixe body weight.
The thickness of coating slurry in the every one side of polypropylene matrix is 25-35 μm.
Dispersant is surfactant blend.
The granularity of barium sulfate particle after ball milling is between 500-700nm.
The beneficial effects of the invention are as follows：Using ceramic modified polyolefin porous membrane prepared by preparation method of the present invention, have
Electrolyte retention is high, thermal dimensional stability is good, porosity is high, conductivity is high.The battery of power aluminum cell can be effectively improved
Performance and security performance.
Specific implementation mode
A kind of dynamic lithium battery preparation method of ceramic modified polyolefin porous membrane, includes the following steps：1, by sulfuric acid
Barium powder and (C2H2F2) n are separately added into C5H9NO, form a concentration of 5.6-6.3% of barium sulfate, the concentration of (C2H2F2) n
For the mixed liquor of 2.4-2.7%, dispersant is added in mixed liquor, mixed liquor is stirred using magnetic stirring apparatus；2, magnetic force stirs
Centrotheca is formed after mixing 2 hours, centrotheca is subjected to ball milling 2 hours, obtains coating slurry；3, polypropylene matrix is soaked in ethanol
It steeps and is ultrasonically treated, dried；4, coating slurry is coated uniformly on to the two sides of polypropylene matrix using dip-coating method；5,
It dries at room temperature, is finally dried in vacuo 24 hours under the conditions of 60 DEG C, obtains ceramic modified polyolefin porous membrane.Dispersant
Weight is the 2% of blanc fixe body weight.The thickness of coating slurry in the every one side of polypropylene matrix is 32 μm.Sulphur after ball milling
The granularity of sour titanate particle is between 500-700nm.
Ceramic modified polyolefin porous membrane obtained above is detected analysis：
（1）Thermal performance test：By the matrix diaphragm of ceramic modified polyolefin porous membrane and the uncoated coating slurry of the present invention into
Row thermal performance test compares.The ceramic modified polyolefin porous membrane of the present invention is in 120 DEG C, 140 DEG C, 160 DEG C of heat treatment after-contraction
Rate is respectively：0%,6.5%,15.0%.And matrix diaphragm is respectively in 120 DEG C, 140 DEG C, 160 DEG C of heat treatment post-shrinkage ratios：11.6
%,20.0 %,37.8 %.The thermal contraction of matrix diaphragm mainly appears on draw direction rather than draw direction upper diaphragm is being heat-treated
Change in size afterwards is little.BaSO4 ceramic powders are a kind of inorganic particles that thermal stability is splendid, by after immersion coating its
The distribution of continuous uniform is formed on the surface of diaphragm, ceramic powder and basis material are bonded together by PVDF, in matrix diaphragm
When being heat-shrinked, rises and inhibit contraction well.Thermal performance test shows to compare base by the modified diaphragm of ceramic coated
Body diaphragm has better thermal dimensional stability, is conducive to the promotion of dynamic lithium battery security performance.
（2）Close electrolyte performance test：Since the polarity of water is similar to electrolyte polarity, using hydrophilic contact angle come
Characterization.The contact angle that metacneme is modified by ceramic coated is 59.5 ± 5.5o, and the hydrophilic contact angle of matrix diaphragm is
The hydrophilic contact angle of 114.5 ± 2.2o, modified metacneme significantly reduce.The introducing of ceramic powder makes matrix membrane surface be rich in hydroxyl
Base group is changed into hydrophilic surface by hydrophobic surface.Electrolyte retention is another of diaphragm parent's electrolyte performance
Characterizing method, electrolyte retention test result are shown：The electrolyte retention of matrix diaphragm is 144.3% ± 3.0%, this ceramics
The electrolyte retention of improved polyalkene perforated membrane is 211% ± 3.0%.The electrolyte retention of modified metacneme dramatically increases,
The introducing that its reason is attributed to ceramic powder improves the close electrolyte performance of membrane surface first, secondly nanometer in ceramic coating
A large amount of pore structure can be formed between powder, can also possess a certain amount of electrolyte.From diaphragm porosity test data energy
The porosity of enough presence for illustrating this pore structure well, modified metacneme is 45%, and 4% is improved than matrix diaphragm.
（3）Electrochemical property test：The lithium ion conductivity of metacneme before modified is surveyed by AC impedance method
Examination, the experimental results showed that, the impedance value of this ceramic modified polyolefin porous membrane is 3.2 Ω, and the impedance value of matrix diaphragm is
18.8 Ω further calculate to obtain this ceramic modified polyolefin porous membrane conductivity under the abundant adsorbed state of electrolyte to be 0.52
× 10-3 S/cm, and the conductivity of matrix diaphragm is 0.07 × 10-3S/cm.Ceramic coated metacneme porosity improves, to electricity
It solves the affine performance of matter to improve, its electrolyte retention is made to be promoted, reduce lithium ion and conduct suffered resistance in diaphragm.Every
Although the original pore structure of film is covered by ceramic coating, the tiny pore structure in coating between powder can possess a large amount of electrolysis
The conduction that matter is lithium ion in ceramic coating provides a large amount of channels.Modified diaphragm conductivity is obviously improved, and is conducive to obtain
Better battery performance.
The preferred embodiment of the present invention has been described in detail above, it should be understood that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations, therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be in the protection domain being defined in the patent claims.
Claims (5)
1. a kind of dynamic lithium battery preparation method of ceramic modified polyolefin porous membrane, which is characterized in that include the following steps：
1, barium sulfate powder and (C2H2F2) n are separately added into C5H9NO, form a concentration of 5.6-6.3%, (C2H2F2) of barium sulfate
The mixed liquor of a concentration of 2.4-2.7% of n is added dispersant in mixed liquor, is stirred to mixed liquor using magnetic stirring apparatus；
2, magnetic agitation forms centrotheca after 2 hours, and centrotheca is carried out ball milling 2 hours, obtains coating slurry；3, polypropylene matrix is existed
It impregnates and is ultrasonically treated in ethyl alcohol, dried；4, coating slurry is coated uniformly on polypropylene matrix using dip-coating method
Two sides；5, it dries at room temperature, is finally dried in vacuo 24 hours under the conditions of 60 DEG C, obtains ceramic modified polyolefin porous
Film.
2. the dynamic lithium battery as described in claim 1 preparation method of ceramic modified polyolefin porous membrane, which is characterized in that
The weight of the dispersant is the 2% of blanc fixe body weight.
3. the dynamic lithium battery as described in claim 1 preparation method of ceramic modified polyolefin porous membrane, which is characterized in that
The thickness of coating slurry in the every one side of the polypropylene matrix is 25-35 μm.
4. the dynamic lithium battery as described in claim 1 preparation method of ceramic modified polyolefin porous membrane, which is characterized in that
The dispersant is surfactant blend.
5. the dynamic lithium battery as described in claim 1 preparation method of ceramic modified polyolefin porous membrane, which is characterized in that
The granularity of barium sulfate particle after ball milling is between 500-700nm.
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| CN201810585730.0A CN108807790A (en) | 2018-06-08 | 2018-06-08 | A kind of preparation method of the ceramic modified polyolefin porous membrane of dynamic lithium battery |
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| CN201810585730.0A CN108807790A (en) | 2018-06-08 | 2018-06-08 | A kind of preparation method of the ceramic modified polyolefin porous membrane of dynamic lithium battery |
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| CN101814590A (en) * | 2010-04-23 | 2010-08-25 | 湖南业翔晶科新能源有限公司 | Porous solid membrane used for lithium ion battery and production method thereof |
| CN102751463A (en) * | 2012-07-15 | 2012-10-24 | 湛江市鑫满矿业有限公司 | Lithium-ion power battery isolating membrane and preparation method thereof |
| CN103545475A (en) * | 2013-10-29 | 2014-01-29 | 淄博众品鑫化学膜应用技术有限公司 | Barium sulfate diaphragm of lithium ion battery and preparation method thereof |
| CN103779523A (en) * | 2012-10-26 | 2014-05-07 | 海洋王照明科技股份有限公司 | Battery diaphragm and preparation method thereof, and electrochemical capacitor |
| CN104157810A (en) * | 2013-05-15 | 2014-11-19 | 比亚迪股份有限公司 | Diaphragm, preparation method of diaphragm and lithium ion battery |
| CN104584267A (en) * | 2013-02-12 | 2015-04-29 | 三星Total株式会社 | Organic/inorganic composite coating porous separator and secondary battery element using same |
| CN105895844A (en) * | 2016-04-15 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Viscous ceramic diaphragm and preparation method thereof |
| CN105990551A (en) * | 2015-01-28 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Composite separator membrane, preparation method thereof, and application thereof in lithium ion batteries |
| WO2016165633A1 (en) * | 2015-04-14 | 2016-10-20 | Byd Company Limited | Polymer composite membrane and preparation method thereof, gel electrolyte and lithium ion battery having the same |
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2018
- 2018-06-08 CN CN201810585730.0A patent/CN108807790A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101814590A (en) * | 2010-04-23 | 2010-08-25 | 湖南业翔晶科新能源有限公司 | Porous solid membrane used for lithium ion battery and production method thereof |
| CN102751463A (en) * | 2012-07-15 | 2012-10-24 | 湛江市鑫满矿业有限公司 | Lithium-ion power battery isolating membrane and preparation method thereof |
| CN103779523A (en) * | 2012-10-26 | 2014-05-07 | 海洋王照明科技股份有限公司 | Battery diaphragm and preparation method thereof, and electrochemical capacitor |
| CN104584267A (en) * | 2013-02-12 | 2015-04-29 | 三星Total株式会社 | Organic/inorganic composite coating porous separator and secondary battery element using same |
| CN104157810A (en) * | 2013-05-15 | 2014-11-19 | 比亚迪股份有限公司 | Diaphragm, preparation method of diaphragm and lithium ion battery |
| CN103545475A (en) * | 2013-10-29 | 2014-01-29 | 淄博众品鑫化学膜应用技术有限公司 | Barium sulfate diaphragm of lithium ion battery and preparation method thereof |
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| WO2016165633A1 (en) * | 2015-04-14 | 2016-10-20 | Byd Company Limited | Polymer composite membrane and preparation method thereof, gel electrolyte and lithium ion battery having the same |
| CN105895844A (en) * | 2016-04-15 | 2016-08-24 | 合肥国轩高科动力能源有限公司 | Viscous ceramic diaphragm and preparation method thereof |
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Application publication date: 20181113 |
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