CN208706747U - A kind of lithium ion battery ceramic coating membrane - Google Patents
A kind of lithium ion battery ceramic coating membrane Download PDFInfo
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- CN208706747U CN208706747U CN201821592279.7U CN201821592279U CN208706747U CN 208706747 U CN208706747 U CN 208706747U CN 201821592279 U CN201821592279 U CN 201821592279U CN 208706747 U CN208706747 U CN 208706747U
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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 discloses a kind of lithium ion battery ceramic coating membranes, belong to lithium ion battery separator production technical field, including polyalcohol stephanoporate basement membrane, the polymer glue coated on membrane surface side or two sides, the ceramic coating coated on polymer glue surface and the PVDF coated on ceramic coating surface and the membrane surface other side and its copolymerization composition glue liquid.The structure design of the utility model ceramic coating membrane can increase the cohesive force of ceramic coating Yu polyalcohol stephanoporate basement membrane, improve the adhesion strength of diaphragm and positive/negative plate, the problem of effectively improving picking and coating shedding, the efficient Automated assembly of lithium battery is realized, also the significant increase heat resistance of diaphragm and resistance to electrochemical stability.
Description
Technical field
The utility model relates to lithium ion battery separator production technical field, in particular to a kind of lithium ion battery ceramics
Coat diaphragm.
Background technique
In recent years, for reply auto industry grow rapidly bring environmental pollution, petroleum resources sharply consume etc. it is negative
Face is rung, and each state is all actively developing the electric car using clean energy resource.Wherein, lithium ion battery is that electric car is main
Power resources.In addition, application of the lithium ion battery in fields such as 3C, energy storage, power is also very extensive.Diaphragm is lithium ion battery
One of core key material, effect is to separate positive electrode and negative electrode material, allow lithium ion to pass through, electronics is prevented to pass through.Every
The performance of film determines the interfacial structure of electrode, the internal resistance of battery and reservoir quantity etc., and then influences multiplying power, circulation and the peace of battery
The characteristics such as full performance.Diaphragm has vital influence to the performance of actual battery, must have good chemistry, electrification
It learns stability, thermal stability and height wellability is kept to electrolyte during repeated charge.In addition, with electronic vapour
The fast development of vehicle, to the safety of lithium-ion-power cell, more stringent requirements are proposed, and influences lithium-ion-power cell peace
One of the key factor of full property is exactly the safety of diaphragm.The problems such as that there are fusing points is low for conventional polyolefin diaphragm, bad mechanical property,
For lithium ion battery in long-term cyclic process, lithium metal deposition easily forms Li dendrite, and Li dendrite puncture diaphragm will cause positive and negative
It extremely directly contacts, causes short circuit.Equally, overcharge or temperature increase when (100 DEG C or more) can be heat-shrinked, to lead
Cause the safety problems such as battery short circuit, on fire.In addition, causing it to electrolyte due to the hydrophobic performance of polyalkene diaphragm itself
Infiltration and retention are poor, increase impedance, limit the cycle performance of lithium battery high rate charge-discharge performance and lithium battery.
Now by the way that its thermal stability, shrinkage and imbibition can be effectively improved in conventional membrane surface coated ceramic coating
Property, to realize the purpose for improving battery security and chemical property.There is no polar group, surface energy in polyolefin resin
It is low, certain difficulty is attached with for general coating.In addition, ceramics used in common ceramic coating are nano-oxide grain
Son, specific surface energy is big, high surface activity, and single ultra-fine grain often plays pendulum, because mutually inhaling between particle
Draw and reunite, be not easy to disperse, and its surface is generally water-wet behavior, and polyolefin film is hydrophobic material, therefore, ceramic powder applies
The uniformity of cloth is poor, and adhesion strength between the two is lower, there is apparent " picking " phenomenon, this can greatly influence ceramics
Service performance of the diaphragm in lithium ion battery.
In addition, as the ceramic object of coating, using single partial size in current ceramic coating membrane, causing one
The case where kind is high-densit, low hole.Cause the diaphragm gas permeability loss of coating front and back larger, enough storage electrolysis cannot be provided
The space of liquid and high temperature resistance, lithium ion conduction is low, and the high rate performance and cycle performance of final lithium ion battery are bad, no
It can be suitably used for high-end light the 3C digital product and power vehicle of present high speed development.
The patent of Publication No. CN207165671U discloses a kind of ceramic coating membrane of high security, including polyolefin
Base membrane layer and alkaline ceramic coating coated in single or double in polyolefin base membrane are crosslinked with alkane on the alkaline ceramic coating
Base or alkenyl phenyl maleimide high molecular polymer, the polyolefin-based film layer with a thickness of 3.00~20.00 μm, it is described
Alkaline ceramic coating layer thickness is 0.1~0.5 μm, and the alkaline ceramic coating surface density is 0.1~2g/m2, the alkaline ceramic
Partial size D50 be 0.1~0.4 μm.The utility model carries out surface to alkaline ceramic by using short alkyl phosphoric acid class and is modified, warp
Verifying, the diaphragm percent thermal shrinkage is high, and imbibition rate is low, and thermostability is poor, influences service performance of the ceramic diaphragm in lithium ion battery.
Summary of the invention
Utility model aims to solve above-mentioned technical problem, provide a kind of lithium ion battery ceramic coated every
Film to the thermal stability of diaphragm, inhales the problems such as electrolyte rate, coating shedding, picking, ceramic particle easy to reunite and has biggish change
It is kind.
To achieve the above object, the utility model uses following technical scheme:
A kind of lithium ion battery ceramic coating membrane, including polyalcohol stephanoporate basement membrane, be coated on the membrane surface one
The polymer glue of side or two sides, the ceramic coating coated on polymer glue surface and be coated on the ceramic coating
The PVDF and its copolymerization composition glue liquid on surface and the membrane surface other side.
Preferably, the polyalcohol stephanoporate basement membrane be dry method PP diaphragm, wet process PE diaphragm, PE and tri- layers of PP it is compound every
One of film, nonwoven cloth diaphragm, electrostatic spinning PI diaphragm.
Preferably, the thickness of the polyalcohol stephanoporate basement membrane is between 3-60 μm；The hole of the polyalcohol stephanoporate basement membrane
Rate is between 25-75%.
Preferably, the polymer glue and PVDF and its copolymerization composition glue liquid coating layer thickness are between 0.5-10 μm.
Preferably, the thickness of ceramic coating is between 1-15 μm.
Compared with prior art, as follows the advantages of the utility model:
The utility model coated polymer glue between polyalcohol stephanoporate basement membrane and ceramic coating can be improved basement membrane with
Adhesion strength between ceramic particle, the problem of avoiding picking and coating shedding.
The caking property of diaphragm and lithium battery pole slice can be enhanced in PVDF and its copolymer glue-line, to realize efficient automatic
Makeup is matched, also the significant increase heat resistance of diaphragm and resistance to electrochemical stability.
The ceramic coating membrane of the utility model preparation is heat-shrinked lower, peel strength height, and imbibition rate is big.It will be originally practical
The diaphragm of novel preparation is made into lithium ion battery respectively, then at normal temperature using 1C multiplying power charge, 1C multiplying power discharging, successively into
Row 500 times circulations, finally calculate its capacity retention ratio, 92% or more.
Detailed description of the invention
The utility model is described further with reference to the accompanying drawing.
Fig. 1 is the basic structure schematic diagram of lithium ion battery ceramic coating membrane prepared by embodiment 1,2,4.Wherein,
1,5 layers are PVDF and its copolymer glue-line, and 2 layers are ceramic coatings, and 3 layers are polymeric adhesive layers, and 4 layers are polyalcohol stephanoporate basement membranes.
Fig. 2 is the basic structure schematic diagram of lithium ion battery ceramic coating membrane prepared by embodiment 3.Wherein, 1,7 layer
It is PVDF and its copolymer glue-line, 2,6 layers are ceramic coatings, and 3,5 layers are polymeric adhesive layers, and 4 layers are polyalcohol stephanoporate basement membranes.
Fig. 3 is the SEM figure of lithium ion battery ceramic coating membrane prepared by the utility model.
Specific embodiment
It elaborates below by specific embodiment to the utility model, it is practical new that following embodiments are merely to illustrate this
Type, but be not used to limit the scope of the utility model, more it is not limited to the protection scope of the utility model.
Embodiment 1
Refering to fig. 1, a kind of lithium ion battery ceramic coating membrane, including polyalcohol stephanoporate basement membrane 4, be coated on the base
The polymer glue 3 of 4 side of film surface, is coated on the ceramics at the ceramic coating 2 coated on 3 surface of polymer glue
First PVDF on 2 surface of coating and its copolymerization composition glue liquid 1 and the 2nd PVDF coated on the 4 surface other side of basement membrane and its altogether
Polymers glue 5.The polyalcohol stephanoporate basement membrane 4 is dry method PP diaphragm.The polyalcohol stephanoporate basement membrane 4 with a thickness of 20 μm；
The porosity of the polyalcohol stephanoporate basement membrane 4 is 45%.The polymer glue 3, the first PVDF and its copolymerization composition glue liquid 1, the
Two PVDF and its coating layer thickness for being copolymerized composition glue liquid 5 are 0.5 μm.The thickness of ceramic coating is 3.5 μm.
Preparation method: by polymer glue using coater in 20 μm of dry method PP membrane surface side, wherein applying
Cloth machine speed is 70m/min, and polymer glue coating thickness is 0.5 μm, after dried by 60 DEG C of baking ovens, winding；Ceramics are applied
Layer slurry is using coater in above-mentioned coating membrane polymer film surface, and wherein coater speed is 60m/min, ceramics
Coating layer thickness is 3.5 μm, after dried by 45 DEG C of baking ovens, winding；PVDF and its copolymerization composition glue liquid are applied respectively using coating machine
It is overlying on the other side of above-mentioned coating diaphragm ceramic coating surface and polyalcohol stephanoporate basement membrane, wherein coater speed is 50m/min,
PVDF and its copolymerization composition glue liquid coating thickness are 0.5 μm, after dried by 40 DEG C of baking ovens, winding；Coating method is the painting of dimple version
Cloth；The ceramic coating membrane overall thickness for finally obtaining lithium ion battery is 25 μm, and specification is 20+5 μm.Wherein 20 μm of dry method PP
Diaphragm porosity is 45%.
Embodiment 2
Refering to fig. 1, a kind of lithium ion battery ceramic coating membrane, including polyalcohol stephanoporate basement membrane 4, be coated on the base
The polymer glue 3 of 4 side of film surface, is coated on the ceramics at the ceramic coating 2 coated on 3 surface of polymer glue
First PVDF on 2 surface of coating and its copolymerization composition glue liquid 1 and the 2nd PVDF coated on the 4 surface other side of basement membrane and its altogether
Polymers glue 5.The polyalcohol stephanoporate basement membrane 4 is dry method PP diaphragm.The polyalcohol stephanoporate basement membrane 4 with a thickness of 16 μm；
The porosity of the polyalcohol stephanoporate basement membrane 4 is 43%.The polymer glue 3, the first PVDF and its copolymerization composition glue liquid 1, the
Two PVDF and its coating layer thickness for being copolymerized composition glue liquid 5 are 1 μm.The thickness of ceramic coating is 6 μm.
Preparation method: by polymer glue using coater in 16 μm of wet process PE membrane surface side, wherein applying
Cloth machine speed is 60m/min, and polymer glue coating thickness is 1.0 μm, after dried by 55 DEG C of baking ovens, winding；Ceramics are applied
Layer slurry is using coater in above-mentioned coating membrane polymer film surface, and wherein coater speed is 20m/min, ceramics
Coating layer thickness is 6.0 μm, after dried by 60 DEG C of baking ovens, winding；PVDF and its copolymerization composition glue liquid are applied respectively using coating machine
It is overlying on the other side of above-mentioned coating diaphragm ceramic coating surface and polyalcohol stephanoporate basement membrane, wherein coater speed 30m/min,
PVDF and its copolymerization composition glue liquid coating thickness are 1.0 μm, after dried by 45 DEG C of baking ovens, winding；Coating method is dip-coating；Finally
The ceramic coating membrane overall thickness for obtaining lithium ion battery is 25 μm, and specification is 16+9 μm.Wherein 16 μm of wet process PE membranes pores
Gap rate is 43%.
Embodiment 3
Referring to Fig.2, a kind of lithium ion battery ceramic coating membrane, including polyalcohol stephanoporate basement membrane 4, it is coated on the base
The first polymer glue 3 of 4 upside of film surface, is coated on the second polymer glue 5 coated on 4 downside of membrane surface
First ceramic coating 2 on 3 surface of first polymer glue, the second pottery coated on 5 surface of second polymer glue
Porcelain coating 6, the first PVDF coated on 2 surface of the first ceramic coating and its copolymerization composition glue liquid 1 are coated on second pottery
2nd PVDF and its copolymerization composition glue liquid 7 on 6 surface of porcelain coating.The polyalcohol stephanoporate basement membrane 4 is wet process PE diaphragm.It is described poly-
Close the porous basement membrane 4 of object with a thickness of 12 μm；The porosity of the polyalcohol stephanoporate basement membrane 4 is 37%.First PVDF and its
It is copolymerized composition glue liquid 1, first polymer glue 3, second polymer glue 5, the 2nd PVDF and its coating layer thickness for being copolymerized composition glue liquid 7
It is 0.5 μm.The thickness of first ceramic coating 2 and the second ceramic coating 6 is 2 μm.
Preparation method: polymer glue is respectively coated using coating machine in 12 μm of wet process PE membrane surface two sides,
Middle coater speed is 80m/min, and polymer glue coating thickness is 0.5 μm, after dried by 65 DEG C of baking ovens, winding；It will pottery
Porcelain coating paste is respectively coated using coating machine in the polymer latex layer surface of above-mentioned coating diaphragm two sides, wherein coater speed
For 40m/min, thickness of ceramic coating is 2.0 μm, after dried by 65 DEG C of baking ovens, winding；PVDF and its copolymerization composition glue liquid are made
Be respectively coated with coating machine in the ceramic coating surface of above-mentioned coating diaphragm two sides, wherein coater speed 70m/min, PVDF and
It is 0.5 μm that it, which is copolymerized composition glue liquid coating thickness, after dried by 65 DEG C of baking ovens, winding；Coating method is transfer type coating；Finally
The ceramic coating membrane overall thickness for obtaining lithium ion battery is 18 μm, and specification is 12+6 μm.Wherein 12 μm of wet process PE membranes pores
Gap rate is 37%.
Embodiment 4
Refering to fig. 1, a kind of lithium ion battery ceramic coating membrane, including polyalcohol stephanoporate basement membrane 4, be coated on the base
The polymer glue 3 of 4 side of film surface, is coated on the ceramics at the ceramic coating 2 coated on 3 surface of polymer glue
First PVDF on 2 surface of coating and its copolymerization composition glue liquid 1 and the 2nd PVDF coated on the 4 surface other side of basement membrane and its altogether
Polymers glue 5.The polyalcohol stephanoporate basement membrane 4 is dry method PP diaphragm.The polyalcohol stephanoporate basement membrane 4 with a thickness of 30 μm；
The porosity of the polyalcohol stephanoporate basement membrane 4 is 55%.The polymer glue 3, the first PVDF and its copolymerization composition glue liquid 1, the
Two PVDF and its coating layer thickness for being copolymerized composition glue liquid 5 are 1 μm.The ceramic coating 2 is with a thickness of 3 μm.
Preparation method: by polymer glue using coater in 30 μm of dry method PP membrane surface side, wherein applying
Cloth machine speed is 50m/min, and polymer glue coating thickness is 1.0 μm, after dried by 45 DEG C of baking ovens, winding；Ceramics are applied
Layer slurry is using coater in above-mentioned coating membrane polymer film surface, and wherein coater speed is 80m/min, ceramics
Coating layer thickness is 3.0 μm, after dried by 70 DEG C of baking ovens, winding；PVDF and its copolymerization composition glue liquid are applied respectively using coating machine
It is overlying on the other side of above-mentioned coating diaphragm ceramic coating surface and polyalcohol stephanoporate basement membrane, wherein coater speed is 40m/min,
PVDF and its copolymerization composition glue liquid coating thickness are 1.0 μm, after dried by 40 DEG C of baking ovens, winding；Coating method is the painting of dimple version
Cloth；The ceramic coating membrane overall thickness for finally obtaining lithium ion battery is 35 μm, and specification is 30+5 μm.Wherein 30 μm of dry method PP
Diaphragm porosity is 55%.
In the utility model embodiment 1-4, ceramic coating slurry is by following mass ratio at being grouped as: inorganic ceramic
Particle 20-40%, the second binder 10-15%, the second dispersing agent 2-10%, the second solvent 25-45%, wetting agent 7-10%, anti-settling agent
2-6%, defoaming agent 2-5%.
The inorganic ceramic particle is aspherical particle；The inorganic ceramic particle is by the first ceramic particle and
Two ceramic particles composition；The partial size of first ceramic particle is 550-1100nm, and the partial size of second ceramic particle is
100-400nm；The mass ratio of first ceramic particle is 60-80%, and the mass ratio of second ceramic particle is 20-
40%.Ceramic particle uses aspherical, multisize particles, can provide the ceramic coating of a kind of low-density, high porosity, can be improved
The imbibition rate of ceramic coating membrane increases lithium ion conduction, the final high rate performance and cycle life for promoting lithium battery.
Diaphragm prepared by above embodiments is made into lithium ion battery respectively, is then charged at normal temperature using 1C multiplying power,
1C multiplying power discharging successively carries out 500 circulations, finally calculates its capacity retention ratio, reach between 92%-94%, peel strength exists
Between 70-78N/m, imbibition rate is between 21-25g/ ㎡, excellent combination property.Fig. 3 be lithium prepared by the embodiment of the present invention 1 from
The SEM of sub- battery ceramic coating membrane schemes；As can be seen that diaphragm impurity prepared by the present invention is less, intergranular degree of purity is opposite
It is higher.
It should be noted that above embodiments are merely intended for describing the technical solutions of the present application, but not for limiting the present application, although reference
The utility model is described in detail in preferred embodiment, those skilled in the art should understand that, it can be to this reality
It is modified or replaced equivalently with novel technical solution, without departing from the spirit and scope of the technical scheme of the present invention,
It should all cover in the scope of the claims of the utility model.
Claims (5)
1. a kind of lithium ion battery ceramic coating membrane, which is characterized in that including polyalcohol stephanoporate basement membrane, be coated on the base
It the polymer glue of film surface side or two sides, the ceramic coating coated on polymer glue surface and is coated on described
The PVDF and its copolymerization composition glue liquid of ceramic coating surface and the membrane surface other side.
2. lithium ion battery ceramic coating membrane according to claim 1, which is characterized in that the polyalcohol stephanoporate
Basement membrane is dry method PP diaphragm, in wet process PE diaphragm, tri- layers of composite diaphragm of PE and PP, nonwoven cloth diaphragm, electrostatic spinning PI diaphragm
It is a kind of.
3. lithium ion battery ceramic coating membrane according to claim 1, which is characterized in that the polyalcohol stephanoporate base
The thickness of film is between 3-60 μm；The porosity of the polyalcohol stephanoporate basement membrane is between 25-75%.
4. lithium ion battery ceramic coating membrane according to claim 1, which is characterized in that the polymer glue
And PVDF and its copolymerization composition glue liquid coating layer thickness are between 0.5-10 μm.
5. lithium ion battery ceramic coating membrane according to claim 1, which is characterized in that the ceramic coating is thick
Degree is between 1-15 μm.
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| CN201821592279.7U CN208706747U (en) | 2018-09-28 | 2018-09-28 | A kind of lithium ion battery ceramic coating membrane |
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| CN201821592279.7U CN208706747U (en) | 2018-09-28 | 2018-09-28 | A kind of lithium ion battery ceramic coating membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113451708A (en) * | 2020-03-26 | 2021-09-28 | 广州汽车集团股份有限公司 | Functional coating diaphragm and preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof |
| CN114006048A (en) * | 2021-10-25 | 2022-02-01 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| CN114006127A (en) * | 2021-12-30 | 2022-02-01 | 湖南中锂新材料科技有限公司 | Lithium battery diaphragm containing porous PVDF resin coating and preparation method thereof |
| CN114361713A (en) * | 2022-03-11 | 2022-04-15 | 宁德卓高新材料科技有限公司 | Nano coating, diaphragm with nano coating, preparation method of diaphragm and application of diaphragm |
-
2018
- 2018-09-28 CN CN201821592279.7U patent/CN208706747U/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113451708A (en) * | 2020-03-26 | 2021-09-28 | 广州汽车集团股份有限公司 | Functional coating diaphragm and preparation method thereof, lithium ion battery cell, lithium ion battery pack and application thereof |
| CN114006048A (en) * | 2021-10-25 | 2022-02-01 | 珠海冠宇电池股份有限公司 | Battery with a battery cell |
| CN114006048B (en) * | 2021-10-25 | 2023-12-26 | 珠海冠宇电池股份有限公司 | Battery cell |
| CN114006127A (en) * | 2021-12-30 | 2022-02-01 | 湖南中锂新材料科技有限公司 | Lithium battery diaphragm containing porous PVDF resin coating and preparation method thereof |
| WO2023123423A1 (en) * | 2021-12-30 | 2023-07-06 | 中材锂膜有限公司 | Lithium battery separator comprising porous pvdf-based resin coating and preparation method therefor |
| CN114361713A (en) * | 2022-03-11 | 2022-04-15 | 宁德卓高新材料科技有限公司 | Nano coating, diaphragm with nano coating, preparation method of diaphragm and application of diaphragm |
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