CN106711377A - High-performance lithium battery diaphragm and preparation method thereof - Google Patents
High-performance lithium battery diaphragm and preparation method thereof Download PDFInfo
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- CN106711377A CN106711377A CN201611042775.0A CN201611042775A CN106711377A CN 106711377 A CN106711377 A CN 106711377A CN 201611042775 A CN201611042775 A CN 201611042775A CN 106711377 A CN106711377 A CN 106711377A
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- lithium battery
- battery diaphragm
- performance lithium
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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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a high-performance lithium battery diaphragm and a preparation method thereof. The high-performance lithium battery diaphragm comprises an inner layer, a middle layer and an outer layer, wherein the inner layer is a gelled microporous polymer film, the middle layer is a porous polymer film and the outer layer is the gelled microporous polymer film. The preparation method comprises steps of material blending, extruding, composite molding, sheet casting, cooling setting, two-way synchronous drawing, extracting and drying, transverse stretching for expansion and on-line rolling. The prepared lithium battery diaphragm has better high-temperature resistance, the liquid absorption and retention capacity is improved remarkably, the self-discharge rate is reduced, the mechanical properties of the diaphragm are improved, the service life of the lithium battery is prolonged, and the working safety is guaranteed.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of high-performance lithium battery diaphragm and preparation method thereof.
Background technology
In the structure of lithium battery, barrier film is one of crucial interior layer assembly.The performance of barrier film determines the interface of battery
Structure, internal resistance etc., directly affect the characteristics such as capacity, circulation and the security performance of battery, and the barrier film of excellent performance is to improving electricity
The combination property in pond has important effect.The Main Function of barrier film is that the positive and negative electrode for making battery is separated, and prevents the two poles of the earth from connecing
Touch and it is short-circuit, additionally with the function that can pass through electrolyte ion.Barrier film material is nonconducting, its physicochemical properties
Performance to battery has a great impact.The species of battery is different, and the barrier film of use is also different.It is serial for lithium battery, due to
Electrolyte is organic solvent system, so that have the diaphragm material of organic solvent-resistant, it is general using the poly- of high-strength thin-film
Alkene perforated membrane.
With continuing to develop for barrier film industry, the requirement more and more higher of Vehicular battery and high capacity cell to barrier film, mesh
The diaphragm material of preceding in the market can not meet requirement.
The content of the invention
The present invention is to solve the above problems, there is provided a kind of high-performance lithium battery diaphragm and preparation method thereof is solving existing skill
The deficiencies such as barrier film chemistry, mechanical stability poor performance in art.
The technical problems to be solved by the invention are realized using following technical scheme：
A kind of high-performance lithium battery diaphragm, including internal layer, intermediate layer, outer layer, the internal layer are gel microporous polymer membranes,
Intermediate layer is apertured polymeric film, and outer layer is gel microporous polymer membranes.
The gel microporous polymer membranes are made up of the raw material of following weight portion：
Polypropylene 30-40 parts, polyphthalamide 3-5 parts, 2-4 parts of polyphenylene sulphone resin, PEO 1-3
Part, polyarylate 0.5-0.8 parts, pearl essence 0.6-1.0 parts, jelly wax 1.2-1.5 parts, mica powder 0.4-0.6 parts, crystal soil 0.7-
0.9 part, titanium dioxide 0.5-0.8 parts, Graphene 0.3-0.6 parts, asbestos fibre 0.2-0.3 parts, lithopone 0.1-0.3 parts.
The apertured polymeric film is made up of the raw material of following weight portion：
Polypropylene 45-55 parts, ethyl acrylate copolymer 2-5 parts, expanded polystyrene (EPS) 2-3 parts, butyl polyacrylate 2-4
Part, talcum powder 0.6-1.4 parts, wood rosin 1.4-2.0 parts, Starex 2-2.5 parts, silica flour 0.8-1.5 parts, porcelain powder 0.5-
1.2 parts.
Transition interface layer is set between the internal layer and intermediate layer, between intermediate layer and outer layer.
The transition interface layer is modified polypropene layer.
The modified polypropene layer adds 30 parts of polybutadiene by polybutadiene toughness reinforcing in every 100 parts of polypropylene.
The polybutadiene is the polybutadiene with end carboxyl.
A kind of preparation method of high-performance lithium battery diaphragm, comprises the following steps：
(1) batching step：Internal layer, outer layer dispensing：It is sufficiently mixed according to the raw material, is obtained mixture A；Intermediate layer
Dispensing：It is sufficiently mixed according to the raw material, is obtained mixture B；
(2) extrusion, composite molding step：Mixture A is obtained into mixture A uniform high temperatures by double screw extruder one to melt
Body；Mixture B is obtained into mixture B uniform high temperature melts by double screw extruder two；Melt A and melt B are respectively through melt
Pump is according to percentage by weight internal layer 10%：Intermediate layer 80%：Outer layer 10% enters compound in three layers of extrusion die after accurately measuring
Shaping；
(3) slab, cooling and shaping step：Temperature is sequentially passed through from the high-temperature fusant of die slit mouthful outflow be respectively 50
DEG C, 40 DEG C, 30 DEG C, to obtain composition after 30 DEG C of four sharp cooling rolls be the extrusion slab of A/B/A；
(4) bi-directional synchronization stretching step：Constitute as the extrusion slab of A/B/A obtains vertical Lapie into bi-directional synchronization stretching-machine
It it is 5 times, horizontal Lapie is 5 times of oil-containing films；
(5) drying steps are extracted：Oil-containing film after stretching enters extraction tank, using dichloromethane extractant by film
White oil extract, the film containing dichloromethane by hot-rolling drying after by dichloromethane volatilization removing obtain three-layer membrane at the beginning of
Level product, heat roller temperature is 20~40 DEG C；
(6) horizontal drawing expanding step：The three-layer membrane Primary product for obtaining by after transverse stretching machine to the three-layer membrane after expanding；
(7) step is wound online：The heat that three-layer membrane after expanding removes inside barrier film after high temperature heat setting device should
Power, the three-layer membrane gone after de-stress obtains lithium battery diaphragm through online winder winding.
Beneficial effects of the present invention are：
(1) lithium battery diaphragm has preferable resistance to elevated temperatures, and imbibition liquid-keeping property significantly rises, self-discharge rate drop
Low, barrier film mechanical performance is improved, and extends the service life of lithium battery, it is ensured that the security of work.
(2) with electronic isolation, it is ensured that the mechanical isolation of both positive and negative polarity；
(3) barrier film electrolyte resistance corrosion, there is enough chemistry and electrochemical stabilities；
(4) it is good to the wellability of electrolyte and with enough imbibition moisture-retaining capacities.
Specific embodiment
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below
Embodiment is closed, the present invention is expanded on further.
Embodiment 1
A kind of high-performance lithium battery diaphragm, including internal layer, intermediate layer, outer layer, the internal layer are gel microporous polymer membranes,
Intermediate layer is apertured polymeric film, and outer layer is gel microporous polymer membranes.
The gel microporous polymer membranes are made up of the raw material of following weight portion：
30 parts of polypropylene, 3 parts of polyphthalamide, 2 parts of polyphenylene sulphone resin, 1 part of PEO, polyarylate
0.5 part, 0.6 part of pearl essence, 1.2 parts of jelly wax, 0.4 part of mica powder, 0.7 part of crystal soil, 0.5 part of titanium dioxide, Graphene 0.3
Part, 0.2 part of asbestos fibre, 0.1 part of lithopone.
The apertured polymeric film is made up of the raw material of following weight portion：
45 parts of polypropylene, 2 parts of ethyl acrylate copolymer, 2 parts of expanded polystyrene (EPS), 2 parts of butyl polyacrylate, talcum powder
0.6 part, 1.4 parts of wood rosin, 2 parts of Starex, 0.8 part of silica flour, 0.5 part of porcelain powder.
Transition interface layer is respectively provided between the internal layer and intermediate layer, between intermediate layer and outer layer.
The transition interface layer is modified polypropene layer.
The modified polypropene layer adds 30 parts of polybutadiene by polybutadiene toughness reinforcing in every 100 parts of polypropylene.
The polybutadiene is the polybutadiene with end carboxyl.
Embodiment 2
A kind of high-performance lithium battery diaphragm, including internal layer, intermediate layer, outer layer, the internal layer are gel microporous polymer membranes,
Intermediate layer is apertured polymeric film, and outer layer is gel microporous polymer membranes.
The gel microporous polymer membranes are made up of the raw material of following weight portion：
35 parts of polypropylene, 4 parts of polyphthalamide, 3 parts of polyphenylene sulphone resin, 2 parts of PEO, polyarylate
0.7 part, 0.8 part of pearl essence, 1.3 parts of jelly wax, 0.5 part of mica powder, 0.8 part of crystal soil, 0.6 part of titanium dioxide, Graphene 0.4
Part, 0.2 part of asbestos fibre, 0.2 part of lithopone.
The apertured polymeric film is made up of the raw material of following weight portion：
50 parts of polypropylene, 4 parts of ethyl acrylate copolymer, 2 parts of expanded polystyrene (EPS), 3 parts of butyl polyacrylate, talcum powder
1.0 parts, 1.7 parts of wood rosin, 2.3 parts of Starex, 1.2 parts of silica flour, 0.8 part of porcelain powder.
Transition interface layer is respectively provided between the internal layer and intermediate layer, between intermediate layer and outer layer.
The transition interface layer is modified polypropene layer.
The modified polypropene layer adds 30 parts of polybutadiene by polybutadiene toughness reinforcing in every 100 parts of polypropylene.
The polybutadiene is the polybutadiene with end carboxyl.
Embodiment 3
A kind of high-performance lithium battery diaphragm, including internal layer, intermediate layer, outer layer, the internal layer are gel microporous polymer membranes,
Intermediate layer is apertured polymeric film, and outer layer is gel microporous polymer membranes.
The gel microporous polymer membranes are made up of the raw material of following weight portion：
40 parts of polypropylene, 5 parts of polyphthalamide, 4 parts of polyphenylene sulphone resin, 3 parts of PEO, polyarylate
0.8 part, 1.0 parts of pearl essence, 1.5 parts of jelly wax, 0.6 part of mica powder, 0.9 part of crystal soil, 0.8 part of titanium dioxide, Graphene 0.6
Part, 0.3 part of asbestos fibre, 0.3 part of lithopone.
The apertured polymeric film is made up of the raw material of following weight portion：
55 parts of polypropylene, 5 parts of ethyl acrylate copolymer, 3 parts of expanded polystyrene (EPS), 4 parts of butyl polyacrylate, talcum powder
1.4 parts, 2.0 parts of wood rosin, 2.5 parts of Starex, 1.5 parts of silica flour, 1.2 parts of porcelain powder.
Transition interface layer is respectively provided between the internal layer and intermediate layer, between intermediate layer and outer layer.
The transition interface layer is modified polypropene layer.
The modified polypropene layer adds 30 parts of polybutadiene by polybutadiene toughness reinforcing in every 100 parts of polypropylene.
The polybutadiene is the polybutadiene with end carboxyl.
A kind of preparation method of high-performance lithium battery diaphragm, comprises the following steps：
(1) batching step：Internal layer, outer layer dispensing：It is sufficiently mixed according to the raw material, is obtained mixture A；Intermediate layer
Dispensing：It is sufficiently mixed according to the raw material, is obtained mixture B；
(2) extrusion, composite molding step：Mixture A is obtained into mixture A uniform high temperatures by double screw extruder one to melt
Body；Mixture B is obtained into mixture B uniform high temperature melts by double screw extruder two；Melt A and melt B are respectively through melt
Pump is according to percentage by weight internal layer 10%：Intermediate layer 80%：Outer layer 10% enters compound in three layers of extrusion die after accurately measuring
Shaping；
(3) slab, cooling and shaping step：Temperature is sequentially passed through from the high-temperature fusant of die slit mouthful outflow be respectively 50
DEG C, 40 DEG C, 30 DEG C, to obtain composition after 30 DEG C of four sharp cooling rolls be the extrusion slab of A/B/A；
(4) bi-directional synchronization stretching step：Constitute as the extrusion slab of A/B/A obtains vertical Lapie into bi-directional synchronization stretching-machine
It it is 5 times, horizontal Lapie is 5 times of oil-containing films；
(5) drying steps are extracted：Oil-containing film after stretching enters extraction tank, using dichloromethane extractant by film
White oil extract, the film containing dichloromethane by hot-rolling drying after by dichloromethane volatilization removing obtain three-layer membrane at the beginning of
Level product, heat roller temperature is 20~40 DEG C；
(6) horizontal drawing expanding step：The three-layer membrane Primary product for obtaining by after transverse stretching machine to the three-layer membrane after expanding；
(7) step is wound online：The heat that three-layer membrane after expanding removes inside barrier film after high temperature heat setting device should
Power, the three-layer membrane gone after de-stress obtains lithium battery diaphragm through online winder winding.
General principle of the invention, principal character and advantages of the present invention has been shown and described above.The technology of the industry
It should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification is only the present invention to personnel
Preference, be not intended to limit the present invention, without departing from the spirit and scope of the present invention, the present invention also have it is various
Changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by institute
Attached claims and its equivalent thereof.
Claims (8)
1. a kind of high-performance lithium battery diaphragm, it is characterised in that including internal layer, intermediate layer, outer layer, the internal layer is gel micropore
Polymer film, intermediate layer is apertured polymeric film, and outer layer is gel microporous polymer membranes.
2. high-performance lithium battery diaphragm as claimed in claim 1, it is characterised in that the gel microporous polymer membranes are by following
The raw material composition of weight portion：
Polypropylene 30-40 parts, polyphthalamide 3-5 parts, 2-4 parts of polyphenylene sulphone resin, gathers by PEO 1-3 parts
Aromatic ester 0.5-0.8 parts, pearl essence 0.6-1.0 parts, jelly wax 1.2-1.5 parts, mica powder 0.4-0.6 parts, crystal soil 0.7-0.9
Part, titanium dioxide 0.5-0.8 parts, Graphene 0.3-0.6 parts, asbestos fibre 0.2-0.3 parts, lithopone 0.1-0.3 parts.
3. high-performance lithium battery diaphragm as claimed in claim 1, it is characterised in that the apertured polymeric film is by following weight
The raw material composition of part：
Polypropylene 45-55 parts, ethyl acrylate copolymer 2-5 parts, expanded polystyrene (EPS) 2-3 parts, butyl polyacrylate 2-4 parts,
Talcum powder 0.6-1.4 parts, wood rosin 1.4-2.0 parts, Starex 2-2.5 parts, silica flour 0.8-1.5 parts, porcelain powder 0.5-1.2
Part.
4. high-performance lithium battery diaphragm as claimed in claim 1, it is characterised in that between the internal layer and intermediate layer, it is middle
Transition interface layer is respectively provided between layer and outer layer.
5. high-performance lithium battery diaphragm as claimed in claim 4, it is characterised in that the transition interface layer is modified polypropene
Layer.
6. high-performance lithium battery diaphragm as claimed in claim 5, it is characterised in that the modified polypropene layer passes through polybutadiene
Alkene toughness reinforcing, adds 30 parts of polybutadiene in every 100 parts of polypropylene.
7. high-performance lithium battery diaphragm as claimed in claim 6, it is characterised in that the polybutadiene is with end carboxyl
Polybutadiene.
8. a kind of preparation method of high-performance lithium battery diaphragm according to claim 1, comprises the following steps：
(1) batching step：Internal layer, outer layer dispensing：It is sufficiently mixed according to the raw material, is obtained mixture A；Intermediate layer is matched somebody with somebody
Material：It is sufficiently mixed according to the raw material, is obtained mixture B；
(2) extrusion, composite molding step：Mixture A is obtained into mixture A uniform high temperature melts by double screw extruder one；
Mixture B is obtained into mixture B uniform high temperature melts by double screw extruder two；Melt A and melt B are pressed through Melt Pump respectively
According to percentage by weight internal layer 10%：Intermediate layer 80%：Outer layer 10% enters composite molding in three layers of extrusion die after accurately measuring；
(3) slab, cooling and shaping step：From the high-temperature fusant of die slit mouthful outflow sequentially pass through temperature be respectively 50 DEG C, 40
DEG C, 30 DEG C, to obtain composition after 30 DEG C of four sharp cooling rolls be the extrusion slab of A/B/A；
(4) bi-directional synchronization stretching step：It is 5 to constitute as the extrusion slab of A/B/A obtains vertical Lapie into bi-directional synchronization stretching-machine
Times, horizontal Lapie is 5 times of oil-containing films；
(5) drying steps are extracted：Oil-containing film after stretching enters extraction tank, will be white in film using dichloromethane extractant
Oil is extracted, and by obtaining dichloromethane volatilization removing after hot-rolling drying, three-layer membrane is primary to produce the film containing dichloromethane
Thing, heat roller temperature is 20~40 DEG C；
(6) horizontal drawing expanding step：The three-layer membrane Primary product for obtaining by after transverse stretching machine to the three-layer membrane after expanding；
(7) step is wound online：Three-layer membrane after expanding removes the thermal stress inside barrier film after high temperature heat setting device, goes
Three-layer membrane after de-stress obtains lithium battery diaphragm through online winder winding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611042775.0A CN106711377A (en) | 2016-11-24 | 2016-11-24 | High-performance lithium battery diaphragm and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611042775.0A CN106711377A (en) | 2016-11-24 | 2016-11-24 | High-performance lithium battery diaphragm and preparation method thereof |
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| CN106711377A true CN106711377A (en) | 2017-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201611042775.0A Pending CN106711377A (en) | 2016-11-24 | 2016-11-24 | High-performance lithium battery diaphragm and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107978716A (en) * | 2017-11-20 | 2018-05-01 | 南通百正电子新材料股份有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN114784454A (en) * | 2022-06-17 | 2022-07-22 | 宁波长阳科技股份有限公司 | High-temperature-resistant polyolefin microporous membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896856A (en) * | 2012-09-21 | 2013-01-30 | 海南赛诺实业有限公司 | Five-layer coextruded two-way stretch polypropylene polyamide barrier film and manufacturing method thereof |
| CN103618054A (en) * | 2013-11-08 | 2014-03-05 | 青岛中科华联新材料有限公司 | Novel high-temperature-resisting diaphragm of lithium battery and preparation process of diaphragm |
| 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 |
-
2016
- 2016-11-24 CN CN201611042775.0A patent/CN106711377A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896856A (en) * | 2012-09-21 | 2013-01-30 | 海南赛诺实业有限公司 | Five-layer coextruded two-way stretch polypropylene polyamide barrier film and manufacturing method thereof |
| CN103618054A (en) * | 2013-11-08 | 2014-03-05 | 青岛中科华联新材料有限公司 | Novel high-temperature-resisting diaphragm of lithium battery and preparation process of diaphragm |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107978716A (en) * | 2017-11-20 | 2018-05-01 | 南通百正电子新材料股份有限公司 | A kind of lithium battery diaphragm and preparation method thereof |
| CN114784454A (en) * | 2022-06-17 | 2022-07-22 | 宁波长阳科技股份有限公司 | High-temperature-resistant polyolefin microporous membrane and preparation method thereof |
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Application publication date: 20170524 |