CN107978716A - A kind of lithium battery diaphragm and preparation method thereof - Google Patents
A kind of lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN107978716A CN107978716A CN201711158327.1A CN201711158327A CN107978716A CN 107978716 A CN107978716 A CN 107978716A CN 201711158327 A CN201711158327 A CN 201711158327A CN 107978716 A CN107978716 A CN 107978716A
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- layer
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- lithium battery
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- polyolefin layer
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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
-
- 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
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a kind of lithium battery diaphragm, including the first polyolefin layer, intermediate layer and the second polyolefin layer, the intermediate layer is that apertured polymeric film, first polyolefin layer and second polyolefin layer are formed by base layer and spraying with the nano inorganic oxide layer in the base layer.Correspondingly, the invention also discloses a kind of preparation method of lithium battery film, including the preparation process of nano inorganic oxide solution, the preparation process of the first polyolefin layer and the second polyolefin layer, the preparation process in intermediate layer, stretching pore-creating processing step, step is wound online.The lithium battery diaphragm of the present invention has excellent resistance to elevated temperatures, excellent mechanical performance and less shrinking percentage, has expanded the application range of lithium battery isolation membrane.
Description
Technical field
The present invention relates to technical field of lithium batteries, more particularly to a kind of lithium battery diaphragm and preparation method thereof.
Background technology
Lithium ion battery is a kind of new and effective electrochmical power source, has that energy density is big, has extended cycle life, operating voltage
Height, memory-less effect, self discharge are small and the advantages that operating temperature range is wide, are the idealizations of current various portable electronic products
Power supply, and the preferred electrical source of power of following electric automobile are learned, there is wide application space and economic value.
In the structure of lithium battery, membrane is one of crucial interior layer assembly.The performance of membrane determines the interface knot of battery
Structure, internal resistance etc., directly affect the characteristics such as capacity, circulation and the security performance of battery, the membrane of excellent performance is to improving battery
Comprehensive performance have the function that it is important.The main function of membrane is that the positive and negative electrode for making battery is separated, and prevents the two poles of the earth from contacting
And it is short-circuit, additionally have the function of to make electrolyte ion by.Membrane material is nonconducting, its physicochemical properties pair
The performance of battery has a great impact.The species of battery is different, and the membrane of use is also different.For lithium battery series, due to electricity
Solution liquid is organic solvent system, thus needs the diaphragm material of organic solvent-resistant, the general polyene for using high-strength thin-film
Hydrocarbon perforated membrane.
But existing lithium battery diaphragm resistance to elevated temperatures is poor, and mechanical strength is relatively low, and is also easy to produce in the event of high temperatures
Shrink so as to shorten the length of isolation film.
To sum up, a kind of high temperature resistant is researched and developed, lithium battery diaphragm that mechanical strength is higher and shrinking percentage is relatively low and preparation method thereof,
Seem increasingly important.
The content of the invention
It is an object of the invention to for above-mentioned technical problem existing in the prior art, there is provided a kind of lithium battery diaphragm and its
Preparation method.
In order to solve the above-mentioned technical problem, the present invention proposes a kind of lithium battery diaphragm, including the first polyolefin layer, centre
Layer and the second polyolefin layer, the intermediate layer is apertured polymeric film, first polyolefin layer and second polyolefin layer
Formed by base layer and spraying with the nano inorganic oxide layer in the base layer.
Further, the base layer is single-layer polypropylene film.
Further, the nano inorganic oxide layer is silicon dioxide layer, titanium dioxide layer, alumina layer or zinc oxide
Layer.
Further, the intermediate layer is made of the raw material of following parts by weight：80-85 parts of polypropylene, ethyl acrylate are common
3-4 parts of polymers, 3-4 parts of expanded polystyrene (EPS), 3-4 parts of butyl polyacrylate, 1-1.5 parts of talcum powder, 2-3 parts of wood rosin and stone
1-2 parts of English powder.
Correspondingly, present invention also offers a kind of preparation method of lithium battery film, comprise the following steps：
The preparation of S1, nano inorganic oxide solution：Nano inorganic oxide is dissolved in easy volatile solvent and forms nanometer
Inorganic oxide solution, and nano inorganic oxide solution is positioned in nano-oxide sprayer；
The preparation of S2, the first polyolefin layer and the second polyolefin layer：Base layer is unreeled after end releases respectively from respective
It is sent on corresponding nano-oxide sprayer, nano inorganic oxide is carried out to base layer by nano-oxide sprayer
Spray treatment, respectively obtains the first polyolefin layer and the second polyolefin layer；
S3, the preparation in intermediate layer：Apertured polymeric film is prepared according to certain raw material proportioning；
S4, plasma treatment：By obtained first polyolefin layer, the second polyolefin layer and intermediate layer guide roller effect
Under be sent to corresponding plasma processing and carry out plasma treatment；
S5, stretching pore-creating processing：The first polyolefin layer Jing Guo plasma treatment, the second polyolefin layer and intermediate layer are existed
Pooled together under the action of guide roller, and be sent to bi-directional synchronization stretching-machine and carry out stretch processing, wherein, draft temperature is
120-130 DEG C, draw ratio 2.0-4.0；
S6, online winding：By the product in the step S5 after heat setting machine is shaped, wind to obtain through online winder
Lithium battery diaphragm.
Further, the base layer in the step S2 is single-layer polypropylene film.
Further, the easy volatile solvent in the step S1 is acetone or alcohol.
Further, the nano inorganic oxide in the step S1 is silica, titanium dioxide, aluminium oxide or oxidation
Zinc.
Further, in the step S3 apertured polymeric film is prepared according to the raw material proportioning of following parts by weight：It is poly-
80-85 parts of propylene, 3-4 parts of ethyl acrylate copolymer, 3-4 parts of expanded polystyrene (EPS), 3-4 parts of butyl polyacrylate, talcum powder
1-2 parts of 1-1.5 parts, 2-3 parts of wood rosin and silica flour.
Implement the present invention, have the advantages that：
(1) the lithium battery diaphragm resistance to elevated temperatures in the present invention is preferable, its fusing-off temperature is 190-230 DEG C；
(2) the lithium battery diaphragm shrinking percentage in the present invention is relatively low, is only 10-15%；
(3) the lithium battery diaphragm mechanical strength in the present invention is higher, its MD directions tensile strength is 1200-1300kg/
cm2, the tensile strength in TD directions is 180-200kg/cm2；
(4) the lithium battery diaphragm preparation process in the present invention is simple, and cost is relatively low.
Brief description of the drawings
, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical scheme
The attached drawing used is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, right
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings
Its attached drawing.
Fig. 1 is the structure diagram of the lithium battery diaphragm of the present invention.
Wherein, reference numeral corresponds in figure：The first polyolefin layers of 1-, 2- intermediate layers, the second polyolefin layers of 3-.
Embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in inventive embodiments is carried out clear, complete
Ground describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, the every other reality that those of ordinary skill in the art are obtained on the premise of creative work is not made
Example is applied, belongs to the scope of protection of the invention.
Embodiment 1
As shown in Figure 1, the invention discloses a kind of lithium battery diaphragm, including the first polyolefin layer 1, intermediate layer 2 and second
Polyolefin layer 3, the intermediate layer 2 be apertured polymeric film, first polyolefin layer 1 and second polyolefin layer 3 by
Base layer and spraying are formed with the nano inorganic oxide layer in the base layer.
Wherein, the base layer is single-layer polypropylene film, and the nano inorganic oxide layer is silicon dioxide layer, titanium dioxide
Titanium layer, alumina layer or zinc oxide, the additive amount of nano inorganic oxide is the 0.3-0.4% of base layer gross weight, in described
Interbed 2 is made of the raw material of following parts by weight：80-85 parts of polypropylene, 3-4 parts of ethyl acrylate copolymer, expanded polystyrene (EPS)
1-2 parts of 3-4 parts, 3-4 parts of butyl polyacrylate, 1-1.5 parts of talcum powder, 2-3 parts of wood rosin and silica flour.
After testing, the membrane in the present embodiment has resistance to elevated temperatures, its fusing-off temperature is 190-230 DEG C, than pure poly- third
The fusing-off temperature of alkene membrane is higher by 23-63 DEG C.Meanwhile the membrane in the present embodiment places 1.5h under 130 test environment
Afterwards, the shrinking percentage in the MD directions of isolation film is only 10-15%, far below the shrinking percentage of commercially available isolation film 37%.In addition, this implementation
Isolation film mechanical strength in example is higher, its MD directions tensile strength is 1200-1300kg/cm2, the tensile strength in TD directions is
180-200kg/cm2。
Embodiment 2
Present embodiment discloses a kind of preparation method of lithium battery film, comprise the following steps：
The preparation of S1, nano inorganic oxide solution：Nano inorganic oxide is dissolved in easy volatile solvent and forms nanometer
Inorganic oxide solution, and nano inorganic oxide solution is positioned in nano-oxide sprayer；
Wherein, the easy volatile solvent in the step S1 is acetone or alcohol, and the nano inorganic oxide is titanium dioxide
Silicon, titanium dioxide, aluminium oxide or zinc oxide；
The preparation of S2, the first polyolefin layer 1 and the second polyolefin layer 3：Base layer is divided from respective unreel after end releases
It is not sent on corresponding nano-oxide sprayer, nano inorganic oxidation is carried out to base layer by nano-oxide sprayer
Thing spray treatment, respectively obtains the first polyolefin layer 1 and the second polyolefin layer 3, wherein, the additive amount of nano inorganic oxide is
The 0.3-0.4% of base layer gross weight；
Wherein, the base layer in the step S2 is single-layer polypropylene film；
S3, the preparation in intermediate layer 2：Apertured polymeric film is prepared according to certain raw material proportioning；
Wherein, in the step S3 apertured polymeric film is prepared according to the raw material proportioning of following parts by weight：Polypropylene
80-85 parts, 3-4 parts of ethyl acrylate copolymer, 3-4 parts of expanded polystyrene (EPS), 3-4 parts of butyl polyacrylate, talcum powder 1-1.5
1-2 parts of part, 2-3 parts of wood rosin and silica flour；
S4, plasma treatment：By obtained first polyolefin layer 1, the second polyolefin layer 3 and intermediate layer 2 in guide roller
Corresponding plasma processing is sent under effect and carries out plasma treatment；
S5, stretching pore-creating processing：By the first polyolefin layer 1 Jing Guo plasma treatment, the second polyolefin layer 3 and intermediate layer
2 pool together under the action of guide roller, and are sent to bi-directional synchronization stretching-machine and carry out stretch processing, wherein, draft temperature
For 120-130 DEG C, draw ratio 2.0-4.0；
S6, online winding：By the product in the step S5 after heat setting machine is shaped, wind to obtain through online winder
The temperature of lithium battery diaphragm, wherein heat setting machine is 140-160 DEG C.
After testing, through this embodiment in the membrane prepared of method there is resistance to elevated temperatures, its fusing-off temperature is
190-230 DEG C, the fusing-off temperature than virgin pp membrane is higher by 23-63 DEG C.Meanwhile the membrane in the present embodiment is in 130 survey
Under test ring border, after placing 1.5h, the shrinking percentage in the MD directions of isolation film is only 10-15%, far below commercially available isolation film 37%
Shrinking percentage.In addition, the isolation film mechanical strength in the present embodiment is higher, its MD directions tensile strength is 1200-1300kg/cm2,
The tensile strength in TD directions is 180-200kg/cm2。
Implement the present invention, have the advantages that：
(1) the lithium battery diaphragm resistance to elevated temperatures in the present invention is preferable, its fusing-off temperature is 190-230 DEG C；
(2) the lithium battery diaphragm shrinking percentage in the present invention is relatively low, is only 10-15%；
(3) the lithium battery diaphragm mechanical strength in the present invention is higher, its MD directions tensile strength is 1200-1300kg/
cm2, the tensile strength in TD directions is 180-200kg/cm2；
(4) the lithium battery diaphragm preparation process in the present invention is simple, and cost is relatively low.
Above disclosed is only several preferred embodiments of the present invention, cannot limit the present invention's with this certainly
Interest field, therefore equivalent variations made according to the claims of the present invention, are still within the scope of the present invention.
Claims (9)
1. a kind of lithium battery diaphragm, it is characterised in that including the first polyolefin layer (1), intermediate layer (2) and the second polyolefin layer
(3), the intermediate layer (2) is apertured polymeric film, first polyolefin layer (1) and second polyolefin layer (3) by
Base layer and spraying are formed with the nano inorganic oxide layer in the base layer.
2. lithium battery diaphragm according to claim 1, it is characterised in that the base layer is single-layer polypropylene film.
3. lithium battery diaphragm according to claim 1, it is characterised in that the nano inorganic oxide layer is silica
Layer, titanium dioxide layer, alumina layer or zinc oxide film.
4. lithium battery diaphragm according to claim 1, it is characterised in that the intermediate layer (2) by following parts by weight original
Material composition：80-85 parts of polypropylene, 3-4 parts of ethyl acrylate copolymer, 3-4 parts of expanded polystyrene (EPS), butyl polyacrylate 3-4
Part, 1-1.5 parts of talcum powder, 2-3 parts of wood rosin and 1-2 parts of silica flour.
5. a kind of preparation method of lithium battery film, it is characterised in that comprise the following steps：
The preparation of S1, nano inorganic oxide solution：Nano inorganic oxide is dissolved in easy volatile solvent and forms nano inorganic
Oxide solution, and nano inorganic oxide solution is positioned in nano-oxide sprayer；
The preparation of S2, the first polyolefin layer (1) and the second polyolefin layer (3)：Base layer is divided from respective unreel after end releases
It is not sent on corresponding nano-oxide sprayer, nano inorganic oxidation is carried out to base layer by nano-oxide sprayer
Thing spray treatment, respectively obtains the first polyolefin layer (1) and the second polyolefin layer (3)；
S3, the preparation of intermediate layer (2)：Apertured polymeric film is prepared according to certain raw material proportioning；
S4, plasma treatment：By obtained first polyolefin layer (1), the second polyolefin layer (3) and intermediate layer (2) in guide roller
Under the action of be sent to corresponding plasma processing and carry out plasma treatment；
S5, stretching pore-creating processing：By the first polyolefin layer (1) Jing Guo plasma treatment, the second polyolefin layer (3) and intermediate layer
(2) pooled together under the action of guide roller, and be sent to bi-directional synchronization stretching-machine and carry out stretch processing, wherein, stretching temperature
Spend for 120-130 DEG C, draw ratio 2.0-4.0；
S6, online winding：By the product in the step S5 after heat setting machine is shaped, wind to obtain lithium electricity through online winder
Pond membrane.
6. the preparation method of lithium battery film according to claim 4, it is characterised in that the base layer in the step S2
For single-layer polypropylene film.
7. the preparation method of lithium battery film according to claim 4, it is characterised in that volatile in the step S1
Solvent is acetone or alcohol.
8. the preparation method of lithium battery film according to claim 4, it is characterised in that the nanometer nothing in the step S1
Machine oxide is silica, titanium dioxide, aluminium oxide or zinc oxide.
9. the preparation method of lithium battery film according to claim 4, it is characterised in that according to as follows in the step S3
The raw material proportioning of parts by weight prepares the apertured polymeric film：80-85 parts of polypropylene, 3-4 parts of ethyl acrylate copolymer, foaming
1-2 parts of 3-4 parts of polystyrene, 3-4 parts of butyl polyacrylate, 1-1.5 parts of talcum powder, 2-3 parts of wood rosin and silica flour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711158327.1A CN107978716A (en) | 2017-11-20 | 2017-11-20 | A kind of lithium battery diaphragm and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711158327.1A CN107978716A (en) | 2017-11-20 | 2017-11-20 | A kind of lithium battery diaphragm and preparation method thereof |
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| CN107978716A true CN107978716A (en) | 2018-05-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429210A (en) * | 2019-07-19 | 2019-11-08 | 厦门长塑实业有限公司 | A kind of polyamide film and its preparation process of lithium battery flexible packaging |
| EP4037045A4 (en) * | 2019-09-27 | 2022-12-28 | Ohki Yamada | Separation membrane for redox flow battery, and method of producing said separation membrane |
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| CN104191774A (en) * | 2014-08-13 | 2014-12-10 | 江苏安瑞达新材料有限公司 | Novel high-temperature-resistant lithium battery diaphragm and preparation process thereof |
| KR20150084637A (en) * | 2014-01-13 | 2015-07-22 | 국립대학법인 울산과학기술대학교 산학협력단 | Micro porous hybrid separator, method for manufacturing the same and electrochemical device containing the same |
| CN106711377A (en) * | 2016-11-24 | 2017-05-24 | 界首市天鸿新材料股份有限公司 | High-performance lithium battery diaphragm and preparation method thereof |
| CN107316969A (en) * | 2010-11-26 | 2017-11-03 | 丰田自动车株式会社 | Rechargeable nonaqueous electrolytic battery |
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2017
- 2017-11-20 CN CN201711158327.1A patent/CN107978716A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| CN107316969A (en) * | 2010-11-26 | 2017-11-03 | 丰田自动车株式会社 | Rechargeable nonaqueous electrolytic battery |
| KR20150084637A (en) * | 2014-01-13 | 2015-07-22 | 국립대학법인 울산과학기술대학교 산학협력단 | Micro porous hybrid separator, method for manufacturing the same and electrochemical device containing the same |
| CN104191774A (en) * | 2014-08-13 | 2014-12-10 | 江苏安瑞达新材料有限公司 | Novel high-temperature-resistant lithium battery diaphragm and preparation process thereof |
| CN106711377A (en) * | 2016-11-24 | 2017-05-24 | 界首市天鸿新材料股份有限公司 | High-performance lithium battery diaphragm and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110429210A (en) * | 2019-07-19 | 2019-11-08 | 厦门长塑实业有限公司 | A kind of polyamide film and its preparation process of lithium battery flexible packaging |
| EP4037045A4 (en) * | 2019-09-27 | 2022-12-28 | Ohki Yamada | Separation membrane for redox flow battery, and method of producing said separation membrane |
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