CN209374542U - A kind of lithium ion battery polymer coating structure - Google Patents
A kind of lithium ion battery polymer coating structure Download PDFInfo
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- CN209374542U CN209374542U CN201821418265.3U CN201821418265U CN209374542U CN 209374542 U CN209374542 U CN 209374542U CN 201821418265 U CN201821418265 U CN 201821418265U CN 209374542 U CN209374542 U CN 209374542U
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- polymer coating
- lithium ion
- coating structure
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- diaphragm
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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 utility model provides a kind of polymer coating structure of lithium ion battery polymer coating diaphragm, and for the structure distribution of the polymer on diaphragm basement membrane, the distribution of polymer mode includes: the salient point being spaced apart, and the dot being sporadicly distributed.The salient point size of the polymer coating structure of the utility model is close with the granularity size of positive and negative anodes about tens microns, and the lithium ion battery being processed into this way will not occur to analyse lithium phenomenon substantially；Using the little particle dot distribution of dispersibility around salient point, easy Electolyte-absorptive after hot pressing plays certain swelling action, and the electrolyte of such free state is less, and security performance is preferable.
Description
Technical field
The utility model relates to chemical cell field, the neck of coated separator used in lithium ion battery is especially related to
Domain.
Background technique
It is positive electrode that lithium ion battery, which is usually using lithium alloy metals oxide, graphite is negative electrode material, using non-
The battery of Water-Electrolyte.The charge and discharge process of lithium ion battery is exactly the insertion and deintercalation process of lithium ion.In the embedding of lithium ion
Enter with during deintercalation, the insertion and deintercalation of simultaneous and lithium ion equivalent electronics are (traditionally positive to be embedded in or take off
Embedding expression, and cathode insertion or de- insert indicate).In charge and discharge process, lithium ion is embedded in back and forth between positive and negative electrode/takes off
Embedding and insertion/de- slotting, is visually known as " rocking chair batteries ".
In the structure of lithium battery, diaphragm is crucial one of interior layer assembly.For lithium battery series, since electrolyte is
Organic solvent system, thus the diaphragm material of organic solvent-resistant is needed, mostly use the polyolefin porous membrane of high-strength thin-film.
The performance of diaphragm determines the interfacial structure of battery, internal resistance etc., directly affects the spies such as capacity, circulation and the security performance of battery
Property, the diaphragm haveing excellent performance plays an important role the comprehensive performance for improving battery.The main function of diaphragm makes battery
Positive and negative electrode is separated, prevent the two poles of the earth contact and it is short-circuit, additionally have the function of electrolyte ion capable of being made to pass through.Diaphragm material
Matter be it is nonconducting, physicochemical properties have a great impact to the performance of battery.The type of battery is different, the diaphragm of use
Also different.For lithium battery series, since electrolyte is organic solvent system, thus the diaphragm material of organic solvent-resistant is needed
Material, the general polyolefin porous membrane for using high-strength thin-film.
Industrial requiring to include for lithium ion battery separator: (1) there is electronic isolation, guarantees the machinery of positive and negative anodes
Isolation；(2) there are certain aperture and porosity, guarantee low resistance and high ionic conductivity, have well thoroughly to lithium ion
The property crossed；(3) since the solvent of electrolyte is highly polar organic compound, the necessary electrolyte resistance corrosion of diaphragm has enoughization
And electrochemical stability；(4) wellability of electrolyte is got well and there is enough imbibition moisture-retaining capacities；(5) have enough
Mechanical property, including puncture strength, tensile strength etc., but thickness is as small as possible；(6) spatial stability and planarization are good；(7)
Thermal stability and to automatically shut down protective value good.Requirement of the power battery to diaphragm is higher, generallys use composite membrane, it is desirable that diaphragm
Heat shrinkable wants small, otherwise can cause short circuit, and then cause battery thermal runaway.
With the rapid development of lithium ion battery industry, the hardness requirement of lithium ion battery is increasingly increased, is polymerize at this time
Object coating diaphragm is gradually recognized.Polymer-coated diaphragm using polyolefins diaphragm as substrate, surface coat one layer it is organic poly-
Object material is closed, is handled by special process and substrate is bonded together, due to the characteristic of its organic polymer material itself, made
Obtaining its coating diaphragm can be bonded together at high temperature under high pressure with battery pole piece, to promote the hardness of battery, reach protection electricity
The effect of core.
The most polymer coated separator used now is divided to two kinds, and one is the coated films of coating uniform distribution, another
It is the coated film being distributed a little louder；The increase that the former causes the ventilative value of ventilated membrane double with the increase of coating layer thickness, resistance increase
Add larger, the adhering performance after pole piece hot pressing is poor；The latter is the coated film of a little bigger (diameter is about at 150 microns or more) distribution,
Battery hardness after assembling is weaker, and at relatively a little bigger place, analysis lithium phenomenon easily occurs.
To overcome drawbacks described above, the utility model provides the polymer on a kind of lithium ion battery polymer coating diaphragm
Coating structure.
Utility model content
To overcome in polymer diaphragm for lithium ion cell in the prior art, the coated film of coating uniform distribution can be with
It is larger that the increase of coating layer thickness causes resistance to increase, and the adhering performance after pole piece hot pressing is poor；And the coated film group being distributed a little louder
Battery hardness after dress is weaker, and at relatively a little bigger place, it may occur that the technical issues of analysing lithium phenomenon, the purpose of this utility model is that
It is proposed that a kind of includes the polymer diaphragm for lithium ion cell around salient point distribution and salient point in the distribution of fragmentary dot.
In order to solve the above technical problems, the utility model adopts the following technical solution.
A kind of polymer coating structure of polymer coating diaphragm, the structure distribution of the polymer on diaphragm basement membrane,
It include: the salient point being spaced apart, and the dot being sporadicly distributed.
The dot is distributed in around the salient point being spaced apart, with salient point composition rule or irregular pattern.
Wherein, the salient point can be various shape, such as rectangular, round, irregular shape etc., circular, ellipse or
Round and smooth rectangular in corner.
Likewise, the dot also can choose various shape, such as rectangular, round, irregular shape etc. is circular, ellipse
Round or round and smooth corner is rectangular.
Convenient for statement, the utility model states the size of salient point and dot all with the circular diameter of same area.
Wherein, the salient point diameter being spaced apart is between 0.005-0.1 millimeters.
Correspondingly, the diameter of the dot being sporadicly distributed is between 0.1-2 microns.
Moreover, the polymer coating with a thickness of between 0.5 to 3 micron.
Generally speaking, the area that the salient point being spaced apart is distributed on lithium ion battery polymer coating diaphragm
It is between 15-40% that lithium ion battery, which is accounted for, with the percentage of the polymer coating diaphragm gross area；
The area that the dot being sporadicly distributed is distributed on lithium ion battery polymer coating diaphragm accounts for lithium ion
Battery is between 25-45% with the percentage of the polymer coating diaphragm gross area.
Wherein, the polymer is Kynoar, polymethyl methacrylate, vinylidene-tetrafluoroethene or inclined fluorine
One of ethylene-hexafluoroethylene or a variety of mixtures.
In addition, the lithium ion battery is made with polymer coating diaphragm of aqueous process recipe, diaphragm basement membrane is adopted
Adhered to single side coating.
Also or, the lithium ion battery is made with polymer coating diaphragm of aqueous process recipe, to diaphragm basement membrane
Adhered to using coated on both sides.
In addition, the diaphragm basement membrane is the multilayer complex films of polypropylene screen or polyethylene film or polypropylene and polyethylene.
The lithium ion battery of the utility model can be used commonly used in the art with the polymer architecture of polymer coating diaphragm
Processing method preparation, such as one of micro- rotogravure application, dipping, printing or hot composition process or a variety of hybrid techniques.
Micro- rotogravure application can be used to realize here, especially set out, by the surface of applicator roll according to concave point and concave point around
The pattern for the small concave point being sporadicly distributed is carved, and then completes to coat with later applicator roll is processed.
Alternatively, selection particle size distribution prepares slurry in the raw material (particle diameter distribution bimodal) of different range, obtain
Slurry endoparticle diameter range concentrates on the slurry of salient point diameter range and dot diameter range substantially, using micro- intaglio plate coating
Mode be transferred on substrate, form salient point and dot and be scattered and be distributed on basilar memebrane.
Using the lithium ion battery polymer coating structure of the utility model, since salient point size is on tens microns of left sides
The right side, close with the granularity size of positive and negative anodes, the lithium ion battery being processed into this way will not occur to analyse lithium phenomenon substantially；In addition its
Surrounding is distributed using the little particle of dispersibility, and easy Electolyte-absorptive after hot pressing plays certain swelling action, such free state
Electrolyte is less, can substantially security performance it is preferable.In addition, the hardness of lithium ion cell being processed into is larger, it is easier to battery pack
Dress.
In addition, using the lithium ion battery polymer coating structure of the utility model, lithium compared with the prior art from
Sub- battery polymer coating structure, value of breathing freely caused by being reduced after coating because of coated film thickness increase, thus ventilative value
Incrementss reduce, and improve the conductivity of lithium battery.
Detailed description of the invention
Fig. 1 is the surface of the anilox roll of the lithium ion battery polymer coating diaphragm of specific embodiment according to the present invention
Pattern schematic diagram.Wherein, 10 be concave point, and 20 be dot.
The Electronic Speculum of polymer architecture on the lithium ion battery polymer coating diaphragm that Fig. 2 obtains for the embodiment of the present invention 1
Photo.
The Electronic Speculum of polymer architecture on the lithium ion battery polymer coating diaphragm that Fig. 3 obtains for the embodiment of the present invention 2
Photo.
The Electronic Speculum of polymer architecture is shone on the lithium ion battery polymer coating diaphragm that Fig. 4 obtains for comparative example of the present invention
Piece.
Specific embodiment
With reference to the accompanying drawing, it elaborates to the utility model.
The detailed example embodiment of following discloses.However, specific structure and function details disclosed herein merely for the sake of
The purpose of example embodiment is described.
It should be appreciated, however, that the utility model is not limited to disclosed particular exemplary embodiment, but covering falls into this public affairs
Open all modifications, equivalent and the alternative in range.In the description to whole attached drawings, identical appended drawing reference indicates identical
Element.
Refering to attached drawing, this specification structure depicted in this specification institute accompanying drawings, ratio, size etc., only to cooperate specification
Revealed content is not intended to limit the utility model enforceable limit so that those skilled in the art understands and reads
Fixed condition, therefore do not have technical essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size, not
It influences still fall in the revealed skill of the utility model under the effect of the utility model can be generated and the purpose that can reach
Art content obtains in the range of capable of covering.Meanwhile cited position restriction term in this specification, it is merely convenient to the bright of narration
, rather than to limit the enforceable range of the utility model, relativeness is altered or modified, and is changing technology without essence
It inside holds, when being also considered as the enforceable scope of the utility model.
Lithium ion battery in specific embodiment of the present invention is with polymer coating coating since salient point size is several
About ten microns, close with the granularity size of positive and negative anodes, it is existing that analysis lithium will not occur substantially for the lithium ion battery being processed into this way
As；And using the little particle dot distribution of dispersibility around it, easy Electolyte-absorptive after hot pressing plays certain swelling and makees
With the electrolyte of such free state is less, and security performance is preferable.
Wherein, the polymer is Kynoar, polymethyl methacrylate, vinylidene-tetrafluoroethene or inclined fluorine
One of ethylene-hexafluoroethylene or a variety of mixtures.
It is Piezoelectricity under Kynoar (PVDF) normality, with excellent chemical corrosion resistance, excellent resistance to
High temperature is color distortion and oxidative resistance.Polymethyl methacrylate code name of abridging is PMMA, has good chemical stability and resistance to
Hou Xing.Vinylidene-tetrafluoroethene or vinylidene-hexafluoroethylene etc. are vinylidene and tetrafluoroethene or hexafluoroethylene respectively
The copolymer of formation has excellent chemical stability, corrosion resistance, leakproofness.These polymer are used as lithium ion battery
The raw material of polymer coating diaphragm, so that coated separator has better chemical stability.
The lithium ion battery is made with polymer coating structure of aqueous process recipe, uses single side to diaphragm basement membrane
Coating attachment；Also or, diaphragm basement membrane is adhered to using coated on both sides.
In addition, the diaphragm basement membrane is the multilayer complex films of polypropylene screen or polyethylene film or polypropylene and polyethylene.
Polypropylene screen is generally multilayer mutual aid film, is by PP GRANULES after co-extrusion forms sheet material, then through in length and breadth two
The stretching in a direction and be made.And the characteristics such as polyethylene film has moisture resistance, and penetrability is small.Polyethylene film according to manufacturing method with
The difference of control means can produce the production of the different performances such as low-density, middle density, highdensity polyethylene and crosslinked polyethylene
Product.Polypropylene screen or polyethylene film all have the characteristic that moisture resistance is good, stability is good, heat sealability is good, are for lithium-ion electric
The ideal substrate of pond polymer coating diaphragm.
Embodiment 1
The present embodiment is coated with to prepare lithium ion battery polymer coating knot described in the utility model using anilox roll
Structure.
The polymer paste for preparing consistency is realized, wherein net by the dotted anilox roll that size punctum rule designs
The surface of line roller is in the indentation of specific position setting size concave point, and interval 100-800 microns of the size concave point of indentation, pattern is such as
Shown in Fig. 1, using print principle, polymer paste is coated on basement membrane.
As shown in the schematic of Figure 1, using the pattern of anilox roll, under the action of coating pressure, make distribution of polymer by
Concave point 10 in anilox roll, the mode of dot 20 finally make to be scattered in corresponding salient point on diaphragm basement membrane and dot are spaced apart
Polymer structure.
The preparation of waterborne polymeric slurry: 77 parts of deionized waters and 15 parts of polymethyl methacrylates are mixed evenly,
It adds 8 parts of CMC to be mixed evenly, through ball milling 2h, obtains the aqueous mixed slurry of uniform particle sizes；
Coating: using the anilox roll coating of design, the aqueous mixed slurry as made from step 1 is coated on a thickness of 9um
PE film side, formed polymer coating.
What is obtained applies cloth diaphragm through it is equally distributed to obtain big small salient point after temperature is 30-70 DEG C of drying in oven
Polymer coating diaphragm, wherein the thickness of coating is 0.3-2um, and the surface density of coating is 0.8g/m2, electromicroscopic photograph is shown in figure
2。
The thickness of polymer coating needs clearly to control, and increasing if thickness is too thick leads to the ventilative of ventilated membrane
Value.And if too thin, it is difficult to ensure the chemistry and electrochemical stability of polymer coating film.
The salient point diameter being spaced apart is 15 microns, is spaced in 10-50 micron between adjacent salient point
Between.Make the granularity size of salient point and positive and negative anodes close in this way, the lithium ion battery being processed into this way will not analyse substantially
Lithium phenomenon.
The dot size is between 0.1 to a few micrometers.Easy Electolyte-absorptive after dot hot pressing.
Generally speaking, the area that the salient point being spaced apart is distributed on lithium ion battery polymer coating diaphragm
The percentage for accounting for the lithium ion battery polymer coating diaphragm gross area is between 35%, described to be sporadicly distributed around salient point
It is total that the area that dot is distributed on lithium ion battery polymer coating diaphragm accounts for lithium ion battery polymer coating diaphragm
The percentage of area is between 45%.
Embodiment 2
The present embodiment, which is prepared lithium ion battery described in the utility model using the inhomogenous slurry of big small particle and used, to be gathered
Close object coating structure.
Using the polymer of particle diameter distribution bimodal, peak Distribution is located at 5-10 microns and 0.1-1 microns, matches slurrying
Material, the mode by micro- intaglio plate coating are transferred on substrate, are distributed in the two sides of film.
The preparation of waterborne polymeric slurry: 78 parts of deionized waters and 12 parts of Kynoar are mixed evenly, are added
10 parts of CMC are mixed evenly, and obtain the aqueous mixed slurry of stable and uniform；The particle size distribution range control of obtained slurry exists
D50<20um。
Coating: the aqueous mixed slurry as made from step 1 is coated on by the way of micro- intaglio plate coating with a thickness of 20um
PP film two sides, polymer coating is formed, wherein obtaining big small salient point through after temperature is 50 DEG C of drying in oven and being distributed
Polymer coating diaphragm, wherein the overall thickness of coating is 5.3um, and the surface density of coating is 2.5g/m2.Its electromicroscopic photograph is shown in
Fig. 3.The salient point diameter being spaced apart is 8-12 microns, being spaced between 10-50 microns between adjacent salient point.Dot
Size is between 0.1 to 1 micron.
The area that the salient point being spaced apart is distributed on lithium ion battery polymer coating diaphragm accounts for lithium ion
The percentage of the battery polymer coating diaphragm gross area is 25%, and the dot is in lithium ion battery polymer coating diaphragm
On the area that is distributed to account for the percentage of the lithium ion battery polymer coating diaphragm gross area be 45%.
Comparative example:
The preparation of waterborne polymeric slurry: 77 parts of deionized waters and 15 parts of Kynoar are mixed evenly, add 8
Part CMC is mixed evenly, and through ball milling 2h, obtains the aqueous mixed slurry of uniform particle sizes；
Coating: the aqueous mixed slurry as made from step 1 is coated on by the way of micro- intaglio plate coating with a thickness of 20um
PE film side, polymer coating is formed, wherein being evenly distributed through after temperature is 30-70 DEG C of drying in oven
Polymer coating diaphragm, wherein the thickness of coating is 1um, and the surface density of coating is 1.0g/m2。
Its electromicroscopic photograph is shown in Fig. 4.
The sample that above-described embodiment is obtained carries out air permeability (test of Gurley value) test:
At room temperature, pass through 1.0 using Gurley permeating degree tester (Gurley-4110N type) test 100ml gas
The time (second) of the circular surface of square feet is the gas permeability value of diaphragm.
Therefore, by using the diaphragm for lithium ion battery of the polymer coating structure of the utility model, compared to existing
The lithium ion battery of technology polymer coating diaphragm, value of breathing freely caused by being reduced after coating because of coated film thickness increase, because
And the incrementss of ventilative value reduce, and then improve the conductivity of lithium battery.
It should be noted that above embodiment is only the preferable embodiment of the utility model, cannot be understood as
Limitation to scope of protection of the utility model is appointed under without departing from the utility model concept thereof to what the utility model was done
What minor variations and modifications belongs to the protection scope of the utility model.
Claims (7)
1. a kind of lithium ion battery polymer coating structure, the polymer coating structure distribution is special on diaphragm basement membrane
Sign is that the polymer coating structure includes: the salient point being spaced apart, and the dot being sporadicly distributed, the dot distribution
Around the salient point being spaced apart, pattern is formed with salient point.
2. polymer coating structure according to claim 1, which is characterized in that the salient point diameter being spaced apart is big
Small is between 0.005-0.1 millimeters；The diameter of the dot being sporadicly distributed is between 0.1-2 microns.
3. polymer coating structure according to claim 1, which is characterized in that the polymer coating with a thickness of
Between 0.5 to 3 micron.
4. polymer coating structure according to claim 1, which is characterized in that the salient point being spaced apart is polymerizeing
The area being distributed on object coating structure accounts for the percentage of the polymer coating structure gross area between 15-40%.
5. polymer coating structure according to claim 1, which is characterized in that the dot being sporadicly distributed is polymerizeing
The area being distributed on object coating structure accounts for the percentage of the polymer coating structure gross area between 25-45%.
6. polymer coating structure according to claim 1, which is characterized in that the distribution of polymer is in diaphragm basement membrane
Side.
7. polymer coating structure according to claim 1, which is characterized in that the distribution of polymer is in diaphragm basement membrane
Two sides.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201821418265.3U CN209374542U (en) | 2018-08-31 | 2018-08-31 | A kind of lithium ion battery polymer coating structure |
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| CN201821418265.3U CN209374542U (en) | 2018-08-31 | 2018-08-31 | A kind of lithium ion battery polymer coating structure |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301139A (en) * | 2018-08-31 | 2019-02-01 | 上海顶皓新材料科技有限公司 | A kind of lithium ion battery polymer coating diaphragm |
-
2018
- 2018-08-31 CN CN201821418265.3U patent/CN209374542U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301139A (en) * | 2018-08-31 | 2019-02-01 | 上海顶皓新材料科技有限公司 | A kind of lithium ion battery polymer coating diaphragm |
| CN109301139B (en) * | 2018-08-31 | 2024-04-26 | 上海顶皓新材料科技有限公司 | Polymer coating diaphragm for lithium ion battery |
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