CN108807822A - A kind of high security lithium ion battery diaphragm - Google Patents
A kind of high security lithium ion battery diaphragm Download PDFInfo
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- CN108807822A CN108807822A CN201810683175.5A CN201810683175A CN108807822A CN 108807822 A CN108807822 A CN 108807822A CN 201810683175 A CN201810683175 A CN 201810683175A CN 108807822 A CN108807822 A CN 108807822A
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- layer
- ether
- polyphosphazene polymer
- lithium ion
- ion 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
- H01M50/409—Separators, membranes or diaphragms characterised by the 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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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
Abstract
The present invention discloses a kind of high security lithium ion battery diaphragm, belongs to technical field of lithium ion.A kind of lithium ion battery separator of the present invention, the diaphragm middle layer are polyphosphazene polymer olefin layer, are polyphosphazene polymer ether ether ketone layer in polyphosphazene polymer olefin layer upper and lower surface, in polyphosphazene polymer ether ether ketone layer surface ceramic coating layer.The lithium ion battery separator has excellent closed pore performance, when battery core loss of heat, polyolefin layer melts, but polyether-ether-ketone layer has higher fusing point, fusing does not occur and is heat-shrinked, can effectively prevent positive and negative anodes contact and short circuit occurs, while polyether-ether-ketone layer, have the characteristics that high temperature resistant, strong corrosion resistance, chemical stability, anti-flammability and mechanical strength, effectively improves the security performance of battery.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of lithium ion battery separator more particularly to a kind of Gao An
Full property lithium ion battery separator.
Technical background
As global warming and problem of environmental pollution are increasingly serious, it is to solve to restructure the use of energy, develop new energy
One of Critical policies of the above problem.Lithium ion battery because with high-energy density, high voltage, low self-discharge, memory-less effect,
The advantages that long circulation life, environmental protection, it is considered to be develop the key technology of new energy.
Lithium ion battery is made of anode, cathode, diaphragm, electrolyte and shell, and septation can make the positive and negative of battery
Pole is separated, prevent the two poles of the earth contact and it is short-circuit, meanwhile, also have the function of electrolyte ion capable of being made to pass through.The performance of diaphragm
Interfacial structure, the internal resistance etc. for determining battery, directly affect the characteristics such as capacity, cycle and the security performance of battery, performance is excellent
Different diaphragm plays an important role the comprehensive performance for improving battery.
Currently, the diaphragm of market routine is that polyethylene diagrams, polypropylene diaphragm, polypropylene, polyethylene/polypropylene are multiple mostly
Diaphragm is closed, wherein polyethylene and polyacrylic closed pore temperature is respectively 130 DEG C and 165 DEG C, and the temperature for separating electric current is respectively 140
DEG C and 170 DEG C.Conventional polypropylene, polyethylene/polypropylene composite materials diaphragm, although in temperature rise to 130 DEG C, polyethylene starts
Closed pore, fusing, partition electric current, polypropylene separates positive and negative anodes, but under conditions of reality, battery thermal runaway occurs in temperature
It rises comparatively fast, polypropylene can also melt, and cause battery plus-negative plate that short circuit occurs, and then battery is caused burning to occur or peace of exploding
Full accident.
Documents 1：A kind of macromolecule inorganic coating lithium ion battery separator, including polyolefin porous membrane and it is overlying on polyene
The coat of hydrocarbon perforated membrane one or both sides prepares the slurry of the coat by the coatings combine calculated in percentage by weight
Object 20-60% and water 40-80% compositions；The wherein described coating composition includes the water soluble polymer calculated according to weight quota
0.1-5 parts of thickener, 0.1-5 parts of aqueous dispersion, 10-90 parts of polymeric particles, 9.7-70 parts of ceramic particle and water based emulsion
0.1-10 parts；The polymeric particles be polyimides, polyphenylene sulfide, aramid fiber resin, PET resin, polyether-ether-ketone, polyether-ketone,
The combination of one or more of polyether ketone ketone, polyetherketoneetherketoneketone, poly (arylene ether nitrile)；The grain size of the polymeric particles is 0.2-
4 μm, specific surface area 2-15m2/g.
Above-mentioned documents 1 are that coat is arranged in the side of polyolefin porous membrane or both sides, are contained in coat poly-
Ether ether ketone and ceramic particle, but it is mainly solving the technical problems that can be suitably used for being conducive to large-scale continuous production.
The present invention is quasi- to propose a kind of battery diaphragm of high safety performance.
Invention content
The technical problem to be solved in the present invention is to provide a kind of high security lithium ion battery diaphragms.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
A kind of high security lithium ion battery diaphragm is provided, the diaphragm includes polyphosphazene polymer olefin layer and is separately positioned on
The first polyphosphazene polymer ether ether ketone layer, the second polyphosphazene polymer ether ether ketone layer in the upper and lower both sides of polyphosphazene polymer olefin layer；
Further include be separately positioned on the first polyphosphazene polymer ether ether ketone layer, the second polyphosphazene polymer ether ether ketone layer outer surface first
Ceramic coating layer, the second ceramic coating layer；
The diaphragm further includes the membranes pores being arranged up and down.
Further,
The polyphosphazene polymer olefin layer is high molecular polythene layer or macromolecule polypropylene layer.
Further,
Polyether-ether-ketone in the first polyphosphazene polymer ether ether ketone layer, the second polyphosphazene polymer ether ether ketone layer is with following point
The high polymer of one of minor structure：
The molecular weight of above-mentioned high polymer is 2,000,000~15,000,000 g/mol.
First polyphosphazene polymer ether ether ketone layer, polyether-ether-ketone in the second polyphosphazene polymer ether ether ketone layer molecular structure it is identical or
It is different.
Further,
Ceramic particle in first ceramic coating layer be aluminium oxide, magnesia, zirconium oxide, zinc oxide, titanium dioxide,
It is one or more in silica, aluminium hydroxide, calcium chloride, cium carbonate nanoparticles.
Further,
Ceramic particle in second ceramic coating layer be aluminium oxide, magnesia, zirconium oxide, zinc oxide, titanium dioxide,
It is one or more in silica, aluminium hydroxide, calcium chloride, cium carbonate nanoparticles.
Ceramic particle in first ceramic coating layer, the second ceramic coating layer is identical or different.
Further,
The whole thickness of the polyphosphazene polymer olefin layer, the first polyphosphazene polymer ether ether ketone layer, the second polyphosphazene polymer ether ether ketone layer
Degree is 8 μm~40 μm.
Further,
The thickness of the polyphosphazene polymer olefin layer is 4~20 μm, the first polyphosphazene polymer ether ether ketone layer, the second macromolecule
The thickness of polyether-ether-ketone layer is 2~10 μm.
Further,
First ceramic coating layer, the second ceramic coating layer thickness be 2 μm~6 μm.
First ceramic coating layer, the second ceramic coating layer thickness can also be arranged to difference according to actual needs.
Further,
The aperture of the membranes pores is 0.02~0.2 μm.
Beneficial effects of the present invention：
High security lithium ion battery diaphragm provided by the invention, using polyether-ether-ketone/polyolefin/polyether-ether-ketone structure,
And in upper and lower surface coated ceramic coating.Polyether-ether-ketone has the physical and chemical performances such as high temperature resistant, chemical resistance corrosion, fusing point
334 DEG C, 132~148MPa of tensile strength；In the case where thermal runaway occurs for battery, polyolefin closed pore (polyolefin layer fusing),
Block electric current, since polyether-ether-ketone fusing point is high, polyether-ether-ketone layer will not melt, can effectively prevent positive and negative anodes contact and
Short circuit occurs.Further, since the flame-retarding characteristic of polyether-ether-ketone itself, high temperature resistant, corrosion-resistant, chemical stability and mechanical strength etc.
Characteristic can significantly promote the security performance of battery core.The ceramic coating layer of diaphragm upper and lower surface can promote the wetting of diaphragm
Performance enhances the imbibition liquid-keeping property of diaphragm, and then promotes the electrical property of battery, meanwhile, ceramic coating layer can be further
Improvement battery security performance.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is a kind of structural schematic diagram of high-safety lithium ion battery diaphragm of the embodiment of the present invention；
Wherein：1- polyphosphazene polymer olefin layers；2-1 the first polyphosphazene polymer ether ether ketone layers；2-2 the second polyphosphazene polymer ether ether ketones
Layer；The first ceramic coating layers of 3-1；The second ceramic coating layers of 3-2.
Specific implementation mode
In order to preferably illustrate the high safety performance of the diaphragm, the present invention is further tested below by specific example
Card.Special to illustrate herein, example is only the more directly description present invention, they are the part of the present invention, cannot be to this hair
Bright composition any restrictions.
Following examples are by taking model 75161227-28Ah soft-package batteries as an example, wherein just extremely ternary material, cathode are
Graphite material.
High-safety lithium ion battery diaphragm provided by the invention, as shown in Figure 1, including：Polyphosphazene polymer olefin layer 1,
It is separately positioned on the first polyphosphazene polymer ether ether ketone layer 2-1, the second high molecular polyether in 1 upper and lower both sides of polyphosphazene polymer olefin layer
Ether ketone layer 2-2；Further include being separately positioned on the first polyphosphazene polymer ether ether ketone layer 2-1, the second polyphosphazene polymer ether ether ketone layer 2-2 appearances
The first ceramic coating layer 3-1 in face, the second ceramic coating layer 3-2；
The diaphragm further includes the membranes pores being arranged up and down (aperture is small, not depending on going out in figure).
Embodiment 1
It is polyether-ether-ketone (the first high molecular polyether ether that the diaphragm of the present embodiment, which uses patent diaphragm of the present invention, membrane configuration,
Ketone layer 2-1)/polyethylene (polyphosphazene polymer olefin layer 1)/polyether-ether-ketone (the second polyphosphazene polymer ether ether ketone layer 2-2) composite construction,
Integral thickness is 16 μm, and specifically, the thickness of the first and second polyphosphazene polymer ether ether ketone layer is 4 μm, the thickness of polyethylene layer is 8 μ
M, the particle in the first and second ceramic coating layer is nano alumina particles, and thickness is 2 μm, and the thickness of entire diaphragm is 20 μ
m；The aperture of membranes pores is 0.02 μm.
By lamination, enter shell, fluid injection, chemical conversion, two envelopes, partial volume process making 75161227-28Ah battery cores, obtains sample 1.
The molecular structure of polyether-ether-ketone is：Molecular weight：2000000~1500
Ten thousand, unit g/mol.
Embodiment 2
It is polyether-ether-ketone (the first high molecular polyether ether that the diaphragm of the present embodiment, which uses patent diaphragm of the present invention, membrane configuration,
Ketone layer 2-1)/polyethylene (polyphosphazene polymer olefin layer 1)/polyether-ether-ketone (the second polyphosphazene polymer ether ether ketone layer 2-2) composite construction,
Integral thickness is 8 μm, and the thickness of specific first and second polyphosphazene polymer ether ether ketone layer is 2 μm, and the thickness of polyethylene layer is 4 μm, the
One, the particle in two ceramic coating layers is nano oxidized silicon particle, and thickness is 6 μm, and the thickness of entire diaphragm is 20 μm；Institute
The aperture for stating membranes pores is 0.2 μm.By lamination, enter shell, fluid injection, chemical conversion, two envelopes, partial volume process making 75161227-28Ah
Battery core obtains sample 2.
The molecular structure of polyether-ether-ketone is the same as embodiment 1.
Embodiment 3
It is polyether-ether-ketone (the first high molecular polyether ether that the diaphragm of the present embodiment, which uses patent diaphragm of the present invention, membrane configuration,
Ketone layer 2-1)/polypropylene (polyphosphazene polymer olefin layer 1)/polyether-ether-ketone (the second polyphosphazene polymer ether ether ketone layer 2-2) composite construction,
Integral thickness is 40 μm, and specifically, the thickness of the first and second polyphosphazene polymer ether ether ketone layer is 12 μm, the thickness of polypropylene layer is 16 μ
M, the particle in the first and second ceramic coating layer is nano-calcium carbonate particles, and thickness is 3 μm, and the thickness of entire diaphragm is 46 μ
m；The aperture of the membranes pores is 0.1 μm.By lamination, enter shell, fluid injection, chemical conversion, two envelopes, partial volume process making 75161227-
28Ah battery cores obtain sample 3.
The molecular structure of polyether-ether-ketone is the same as embodiment 1.
Embodiment 4
It is polyether-ether-ketone (the first high molecular polyether ether that the diaphragm of the present embodiment, which uses patent diaphragm of the present invention, membrane configuration,
Ketone layer 2-1)/polypropylene (polyphosphazene polymer olefin layer 1)/polyether-ether-ketone (the second polyphosphazene polymer ether ether ketone layer 2-2) composite construction,
Integral thickness is 25 μm, and specifically, the thickness of the first and second polyphosphazene polymer ether ether ketone layer is 6 μm, the thickness of polypropylene layer is 13
μm, the particle in the first and second ceramic coating layer is titanium dioxide nanoparticle, and thickness is 4 μm, and the thickness of entire diaphragm is
33 μm, the aperture of the membranes pores is 0.1 μm.By lamination, enter shell, fluid injection, chemical conversion, two envelopes, the making of partial volume process
75161227-28Ah battery cores obtain sample 4.
The molecular structure of polyether-ether-ketone is：Molecular weight：2000000~
15000000, unit g/mol.
Embodiment 5
It is polyether-ether-ketone (the first high molecular polyether ether that the diaphragm of the present embodiment, which uses patent diaphragm of the present invention, membrane configuration,
Ketone layer 2-1)/polypropylene (polyphosphazene polymer olefin layer 1)/polyether-ether-ketone (the second polyphosphazene polymer ether ether ketone layer 2-2) composite construction,
Integral thickness is 30 μm, and specifically, the thickness of the first and second polyphosphazene polymer ether ether ketone layer is 9 μm, the thickness of polypropylene layer is 12
μm, the particle in the first and second ceramic coating layer is nano oxidized magnesium granules, and thickness is 5 μm, and the thickness of entire diaphragm is 40
μm, the aperture of the membranes pores is 0.15 μm.By lamination, enter shell, fluid injection, chemical conversion, two envelopes, the making of partial volume process
75161227-28Ah battery cores obtain sample 5.
The molecular structure of polyether-ether-ketone is the same as embodiment 1.
Embodiment 6
It is polyether-ether-ketone (the first high molecular polyether ether that the diaphragm of the present embodiment, which uses patent diaphragm of the present invention, membrane configuration,
Ketone layer 2-1)/polyethylene (polyphosphazene polymer olefin layer 1)/polyether-ether-ketone (the second polyphosphazene polymer ether ether ketone layer 2-2) composite construction,
Specifically for 15 μm, the thickness of the first and second polyphosphazene polymer ether ether ketone layer is 4 μm to integral thickness, and the thickness of polyethylene layer is 8 μ
M, the particle in the first and second ceramic coating layer is nano zircite particle, and thickness is 5 μm, and the thickness of entire diaphragm is 25 μ
The aperture of m, the membranes pores are 0.2 μm.By lamination, enter shell, fluid injection, chemical conversion, two envelopes, partial volume process making 75161227-
28Ah battery cores obtain sample 6.
The molecular structure of polyether-ether-ketone is：Molecular weight：2000000~1500
Ten thousand, unit g/mol.
Embodiment 7
It is polyether-ether-ketone (the first high molecular polyether ether that the diaphragm of the present embodiment, which uses patent diaphragm of the present invention, membrane configuration,
Ketone layer 2-1)/polyethylene (polyphosphazene polymer olefin layer 1)/polyether-ether-ketone (the second polyphosphazene polymer ether ether ketone layer 2-2) composite construction,
Integral thickness is 20 μm, and specifically, the thickness of the first and second polyphosphazene polymer ether ether ketone layer is 5 μm, the thickness of polyethylene layer is 10
μm, the particle in the first and second ceramic coating layer is nano granular of zinc oxide, and thickness is 4 μm, and the thickness of entire diaphragm is 28
μm, the aperture of the membranes pores is 0.1 μm.By lamination, enter shell, fluid injection, chemical conversion, two envelopes, partial volume process making 75161227-
28Ah battery cores obtain sample 7.
The molecular structure of polyether-ether-ketone is the same as embodiment 1.
Example 8：Comparative example
The present embodiment also uses 5 layers of structure as above-described embodiment, difference lies in：Intermediate tri-layer structure is poly- third
The integral thickness of alkene/polyethylene/polypropylene composite construction, composite construction is 16 μm, the particle in the first, second ceramic coating layer
Also it is nano alumina particles, thickness is 2 μm, and the thickness of entire diaphragm is 20 μm.By lamination, enter shell, fluid injection, chemical conversion,
Two envelopes, partial volume process make 75161227-28Ah battery cores, obtain sample 8.
1 safety test contrast table of table
As can be seen from Table 1：
Lithium ion battery separator provided in an embodiment of the present invention, can by overcharging, short circuit, squeeze, needle pierce, fall etc. it is multinomial
Security performance is tested, and safety is good.This is because diaphragm provided by the invention battery occur thermal runaway in the case of, polyolefin
Closed pore (polyolefin layer fusing) blocks electric current, but since polyether-ether-ketone fusing point is high, polyether-ether-ketone layer will not melt, because
This can effectively prevent positive and negative anodes contact and short circuit occur.Further, since the flame-retarding characteristic of polyether-ether-ketone itself, high temperature resistant,
The characteristics such as corrosion-resistant, chemical stability and mechanical strength can significantly promote the security performance of battery core.Diaphragm upper and lower surface
Ceramic coating layer can promote the wettability of diaphragm, enhance the imbibition liquid-keeping property of diaphragm, and then promote the electrical of battery
Can, meanwhile, ceramic coating layer can further improve the security performance of battery.
The above is specific implementation mode of the invention, but any restrictions cannot be constituted to the present invention, therefore is needed special
It points out, it is every based on the present invention, it is made any modification and is all fallen within the scope of the present invention with improvement.
Claims (10)
1. a kind of high security lithium ion battery diaphragm, which is characterized in that
The diaphragm includes polyphosphazene polymer olefin layer and is separately positioned on the first high score in the upper and lower both sides of polyphosphazene polymer olefin layer
Sub- polyether-ether-ketone layer, the second polyphosphazene polymer ether ether ketone layer；
Further include be separately positioned on the first polyphosphazene polymer ether ether ketone layer, the second polyphosphazene polymer ether ether ketone layer outer surface first ceramics
Coat, the second ceramic coating layer；
The diaphragm further includes the membranes pores being arranged up and down.
2. a kind of high security lithium ion battery diaphragm according to claim 1, which is characterized in that
The polyphosphazene polymer olefin layer is high molecular polythene layer or macromolecule polypropylene layer.
3. a kind of high security lithium ion battery diaphragm according to claim 1, which is characterized in that
The first polyphosphazene polymer ether ether ketone layer is the high polymer with one of following molecular structure：
4. a kind of high security lithium ion battery diaphragm according to claim 1-3 any one, which is characterized in that
Polyether-ether-ketone in the second polyphosphazene polymer ether ether ketone layer is the high polymer with one of following molecular structure：
The molecular weight of above-mentioned high polymer is 2,000,000~15,000,000 g/mol.
5. a kind of high security lithium ion battery diaphragm according to claim 1, which is characterized in that
Ceramic particle in first ceramic coating layer is aluminium oxide, magnesia, zirconium oxide, zinc oxide, titanium dioxide, oxidation
It is one or more in silicon, aluminium hydroxide, calcium chloride, cium carbonate nanoparticles.
6. a kind of high security lithium ion battery diaphragm according to claim 1-3 or 5 any one, which is characterized in that
Ceramic particle in second ceramic coating layer is aluminium oxide, magnesia, zirconium oxide, zinc oxide, titanium dioxide, oxidation
It is one or more in silicon, aluminium hydroxide, calcium chloride, cium carbonate nanoparticles.
7. a kind of high security lithium ion battery diaphragm according to claim 1 or 2, which is characterized in that
The polyphosphazene polymer olefin layer, the first polyphosphazene polymer ether ether ketone layer, the second polyphosphazene polymer ether ether ketone layer integral thickness be 8
μm~40 μm.
8. a kind of high security lithium ion battery diaphragm according to claim 7, which is characterized in that
The thickness of the polyphosphazene polymer olefin layer is 4~20 μm, the first polyphosphazene polymer ether ether ketone layer, the second high molecular polyether
The thickness of ether ketone layer is 2~10 μm.
9. a kind of high security lithium ion battery diaphragm according to claim 1 or 2, which is characterized in that
First ceramic coating layer, the second ceramic coating layer thickness be 2 μm~6 μm.
10. a kind of high security lithium ion battery diaphragm according to claim 1 or 2, which is characterized in that
The aperture of the membranes pores is 0.02~0.2 μm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810683175.5A CN108807822A (en) | 2018-06-28 | 2018-06-28 | A kind of high security lithium ion battery diaphragm |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810683175.5A CN108807822A (en) | 2018-06-28 | 2018-06-28 | A kind of high security lithium ion battery diaphragm |
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| CN108807822A true CN108807822A (en) | 2018-11-13 |
Family
ID=64072356
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| CN201810683175.5A Pending CN108807822A (en) | 2018-06-28 | 2018-06-28 | A kind of high security lithium ion battery diaphragm |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110233224A (en) * | 2019-04-09 | 2019-09-13 | 厦门大学 | A kind of heat-proof combustion-resistant diaphragm and its preparation method and application |
| CN114144930A (en) * | 2019-09-19 | 2022-03-04 | 株式会社Lg新能源 | Separator having different porosities in thickness direction and method of manufacturing the same |
| CN114375524A (en) * | 2019-10-21 | 2022-04-19 | 株式会社Lg新能源 | Separator including flame retardant layer and method of manufacturing the same |
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| US20140287296A1 (en) * | 2012-04-30 | 2014-09-25 | Lg Chem, Ltd. | Separator and electrochemical device having the same |
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| CN114144930A (en) * | 2019-09-19 | 2022-03-04 | 株式会社Lg新能源 | Separator having different porosities in thickness direction and method of manufacturing the same |
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Effective date of registration: 20200527 Address after: Room g0232, headquarters building, Changsha Zhongdian Software Park, No. 39, Jianshan Road, high tech Development Zone, Changsha City, Hunan Province Applicant after: Thornton New Energy Technology (Changsha) Co.,Ltd. Address before: 411100 Hunan province Xiangtan City Jiuhua Demonstration Zone No. 78 West Benz Applicant before: SOUNDON NEW ENERGY TECHNOLOGY Co.,Ltd. |
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Application publication date: 20181113 |