CN109935769A - A kind of electrolyte resistance ceramic-coated separator and preparation method thereof - Google Patents
A kind of electrolyte resistance ceramic-coated separator and preparation method thereof Download PDFInfo
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- CN109935769A CN109935769A CN201811637329.3A CN201811637329A CN109935769A CN 109935769 A CN109935769 A CN 109935769A CN 201811637329 A CN201811637329 A CN 201811637329A CN 109935769 A CN109935769 A CN 109935769A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- 239000000919 ceramic Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 97
- 238000005524 ceramic coating Methods 0.000 claims abstract description 47
- 239000011230 binding agent Substances 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 40
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 17
- -1 amino, sulfydryl Chemical group 0.000 claims abstract description 14
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 14
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 7
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 7
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract description 5
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 4
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 19
- 239000002562 thickening agent Substances 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 150000001541 aziridines Chemical class 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 210000004379 membrane Anatomy 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000012982 microporous membrane Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000007763 reverse roll coating Methods 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 230000008595 infiltration Effects 0.000 abstract description 4
- 238000001764 infiltration Methods 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 238000010410 dusting Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 14
- 238000007654 immersion Methods 0.000 description 8
- 239000007767 bonding agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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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- Cell Separators (AREA)
Abstract
This application discloses a kind of electrolyte resistance ceramic-coated separators and preparation method thereof.The electrolyte resistance ceramic-coated separator of the application, including basement membrane and the ceramic coating for being coated on its at least surface, ceramic coating is coated by alumina slurry, binder is polyacrylic acid or derivatives thereof in alumina slurry, or polyacrylate or derivatives thereof, with the crosslinking agent with two or more reactive functionalities, cross-linking reaction is generated；Reactive functionality is at least one of cyanic acid ester group, hydroxyl, carboxyl, epoxy group, amino, sulfydryl, aziridine ternary cyclic group, carbodiimide groups, ester group and derived functionalized groups of these reactive functionalities.The diaphragm of the application can reduce infiltration and swelling of the electrolyte to binder, keep the peel strength of ceramic-coated separator using the cross-linked structure of binder；The fall that diaphragm impregnates peel strength after electrolyte is reduced, dusting problems resulting from is avoided, effectively raises the safety of battery.
Description
Technical field
This application involves battery diaphragm fields, more particularly to a kind of electrolyte resistance ceramic-coated separator and its preparation side
Method.
Background technique
Lithium ion battery have biggish energy density, large current discharging capability is strong, voltage rating is high, has extended cycle life
The advantages that, cycle life can achieve 3000~5000 times under shallow charge and discharge mode.In digital product, electric bicycle, electronic
Multiple industries such as motor, electric car, power energy storage, communication energy storage and field are used widely.
With the extension in lithium ion battery applications field, the requirement to battery security is higher and higher.To improve battery
Safety, while diaphragm is improved to the wellability of electrolyte, resistant to high temperature inorganic or organic grain is coated on polyalkene diaphragm surface
The coating diaphragm of son receives more and more attention.Inorganic particulate coats diaphragm, also known as ceramic-coated separator, wherein with oxidation
Aluminium Al2O3Widely approved and applied for the coating diaphragm of coating.But existing alumina ceramic coating diaphragm,
It will appear the case where peel strength declines to a great extent after impregnating electrolyte, and then be easy to cause picking, and cause a series of safety
Problem.
Summary of the invention
The purpose of the application is to provide a kind of ceramic-coated separator and preparation method thereof of improved electrolyte resistance.
To achieve the goals above, the application uses following technical scheme:
The one side of the application discloses a kind of electrolyte resistance ceramic-coated separator, including basement membrane and is coated on basement membrane
The ceramic coating at least one surface, the ceramic coating are coated with by alumina slurry, the bonding used in alumina slurry
Agent is polyacrylic acid or derivatives thereof or polyacrylate or derivatives thereof, and has two or more reactive functional groups
Group crosslinking agent, cross-linking reaction generate, wherein reactive functionality be cyanic acid ester group, hydroxyl, carboxyl, epoxy group, amino, sulfydryl,
Aziridine ternary cyclic group, carbodiimide groups, ester group and these reactive functionalities derived functionalized groups at least one
Kind.Wherein, derived functionalized groups refer to cyanic acid ester group, hydroxyl, carboxyl, epoxy group, amino, sulfydryl, aziridine ternary cyclic group,
H in carbodiimide groups or ester group is replaced the derived functionalized groups to be formed by alkyl chain.
It should be noted that the electrolyte resistance ceramic-coated separator of the application, it can by the cross-linked structure of binder
To reduce infiltration and swelling of the electrolyte to binder, to maintain peel strength to a greater extent；Avoid aluminium oxide pottery
Peel strength reduces after porcelain coated separator impregnates electrolyte, and the safety problems such as picking thus caused.One kind of the application
In implementation, peel strength fall of the electrolyte resistance ceramic-coated separator after impregnating electrolyte is improved less than 30%
Safety in lithium battery use process.
Preferably, crosslinking agent is epoxy silane, isocyanates, pyridine, aziridines, polycarbodiimide, amino resins
With band at least one of epoxy group resin.
It should be noted that in the application, as long as having two or more reactive functionalities, polypropylene can be made
The crosslinking agent that the derivative of acid, polyacrylate or both crosslinks can be applied to the application；But, it is contemplated that it is viscous
The electrolyte resistance performance of agent is tied, the application is particularly limited to the type of crosslinking agent.
Preferably, in alumina slurry, binder accounts for the 0.5-8% of alumina slurry total weight.
It should be noted that the effect of binder is to be bonded together alumina powder, ceramic coating is formed；Bonding
The content of agent cannot be too low, too low easy not firm, the easy picking of bonding, and the content of binder can not be too high, too Gao Rongyi
Influence the performance of Alumina Ceramics；Therefore, the dosage of the preferred binder of the application is 0.5-8%.
Preferably, the ratio of binder reactive agent and crosslinking agent is between 100:2-100:30.
Preferably, the ratio of binder reactive agent and crosslinking agent is between 100:5-100:20.
It should be noted that binder reactive agent, that is, polyacrylic acid or derivatives thereof or polyacrylate or its spread out
The ratio of biology, binder reactive agent and crosslinking agent depends on the reaction of required crosslinking degree and crosslinking agent itself
The crosslinking ability of functional group or crosslinking agent itself；It is appreciated that the dosage of crosslinking agent is more in the case where crosslinking agent determines,
Before equilibrium is reached, the crosslinking degree of finally formed binder is higher；Specifically, can be according to production or product demand
Depending on, it is not specifically limited herein.
Preferably, in alumina slurry, the specific surface area of alumina powder is less than 14m2/ g, the partial size of alumina powder
For 0.01 μm≤D50≤10 μm.
It is furthermore preferred that the partial size of alumina powder is 0.03 μm≤D50≤3 μm.
It should be noted that the electrolyte resistance ceramic-coated separator of the application, using the binder of cross-linked structure,
The electrolyte resistance performance of ceramic-coated separator is improved, diaphragm is reduced and impregnates the peel strength fall after electrolyte, it is especially suitable
It is less than 14m for specific surface area2The alumina powder that/g, D50 are 0.01-10 μm；The D50 of preferred alumina powder is
0.03-3μm。
Preferably, basement membrane with a thickness of 5-20 μm, porosity 30%-60%, aperture is 0.005-0.15 μm.
Preferably, basement membrane is polyethene microporous membrane, microporous polypropylene membrane or is answered by the multilayer that polyethylene and polypropylene form
Close microporous barrier.
Preferably, ceramic coating with a thickness of 0.5-10 μm.
It preferably, further include at least one of dispersing agent, thickener and surfactant in alumina slurry.
It should be noted that the key of the application is the use of special binders, as other in alumina slurry
Component can refer to existing ceramic coated slurry；For example, dispersing agent, thickener and surfactant can refer to it is existing
Technology.But in order to achieve the effect that preferably to reduce peel strength fall after diaphragm immersion electrolyte, the application couple
Dispersing agent, thickener and surfactant and its dosage are defined respectively, are detailed in following technical scheme.
Preferably, dispersing agent is at least one in Sodium Polyacrylate, ammonium polyacrylate, n-butanol, cyclohexanol and ethyl alcohol
Kind；Thickener is at least one of sodium carboxymethylcellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose；Surface is living
Property agent be ethylene oxide polymer and/or polyether-based polymers.
Preferably, in alumina slurry, dispersing agent accounts for the 0-2% of alumina slurry total weight, and thickener accounts for oxidation aluminium paste
Expect that the 0-5% of total weight, surfactant account for the 0.05-3% of alumina slurry total weight.
The another side of the application discloses the preparation method of the ceramic-coated separator of the application, includes the following steps,
Alumina powder, binder, dispersing agent, thickener and surfactant are mixed in proportion, and be distributed to from
It in sub- water, stirs evenly, obtains alumina slurry；
Lithia slurry is applied to at least one surface of basement membrane, drying processing, i.e. acquisition ceramic coating every
Film.
Preferably, coating specifically using scraper for coating method, Meyer stick rubbing method, reverse roll coating method, intaglio plate roller coating method,
At least one of dip coating and brush application.
Due to using the technology described above, the beneficial effects of the present application are as follows:
The electrolyte resistance ceramic-coated separator of the application can using the cross-linked structure of binder in its ceramic coating
To reduce infiltration and swelling of the electrolyte to binder, to keep the peel strength of ceramic-coated separator to a greater extent；Drop
Low alumina ceramic coating diaphragm impregnates the fall of peel strength after electrolyte, under avoiding peel strength significantly
Dusting problems caused by drop effectively raise the safety of battery.
Specific embodiment
Existing alumina ceramic coating diaphragm is after impregnating electrolyte, and the peel strength of coating can decline to a great extent, this is not
It only will cause picking, influence battery use；And a series of security risk can be generated, for example, coating picking or easily peelable,
The mechanical performance of diaphragm weakens, and stability is poor, is easy to produce the security risks such as explosive spalling.
Present inventor has found after study, if using polyacrylic acid or its derivative in alumina ceramic coating
The cross-linking reaction product of object or polyacrylate or derivatives thereof is as binder, using the cross-linked structure of binder,
Infiltration and swelling of the electrolyte to coating can be not only reduced, but also can effectively keep alumina ceramic coating diaphragm
Peel strength reduces the amplitude that alumina ceramic coating diaphragm impregnates peel strength decline after electrolyte.It is sent out based on the research
Existing, the application creativeness proposes a kind of improved alumina ceramic coating diaphragm, i.e. ceramic coating is applied by alumina slurry
Cloth forms, and the binder used in alumina slurry is polyacrylic acid or derivatives thereof or polyacrylate or its derivative
Object, with the crosslinking agent with two or more reactive functionalities, cross-linking reaction is generated；Wherein, reactive functionality
For ....
The alumina ceramic coating diaphragm of the application, before and after impregnating electrolyte peel strength fall less than 30%,
And peel strength fall of the existing other alumina ceramic coating diaphragms before and after impregnating electrolyte is usually all 50%
Left and right is higher.
The application is described in further detail below by specific embodiment.Following embodiment only carries out the application
It further illustrates, should not be construed as the limitation to the application.
Embodiment 1
This example uses two pack type acrylic bonding agent, prepares alumina ceramic coating diaphragm, wherein alumina powder
For specific surface area 6.8m2The commercially available aluminium oxide that/g, D50 are 0.98 μm, basement membrane are limited purchased from innovative material technology emerging in Shenzhen
14 μm of single layer PP films of company, the porosity of basement membrane are 38%, aperture 27nm.The alumina ceramic coating diaphragm of this example
Preparation method includes:
Binder preparation: binder component A is polyacrylic acid bonding agent, and binder component B is epoxy silane crosslinker,
It needs to be added separately in slurry, A:B weight ratio is 100:10.
Slurry preparation: by deionized water, alumina powder, binder, dispersing agent, thickener, surfactant according to weight
Amount is mixed than 70:29:0.6:0.1:0.22:0.08, is stirred evenly, and alumina slurry is obtained；Wherein dispersing agent is poly- third
Olefin(e) acid sodium, thickener are sodium carboxymethylcellulose, and surfactant is ethylene oxide polymer.
Ceramic-coated separator preparation: the alumina slurry prepared is coated in wherein by PP film using gravure roll method
One surface, coating speed 45m/min, the drying temperature after coating are 50 DEG C, and control coated weight makes final coating layer thickness
It is 2 μm, prepares the alumina ceramic coating diaphragm that overall thickness is 16 μm.
The peel strength of the alumina ceramic coating diaphragm using 180 degree peel strength test method prepared by this example into
Row test, diaphragm Sample Width are 20mm, and puller system is continuously removed with 300mm/min speed.And by the aluminium oxide ceramics of this example
Coated separator soak at room temperature 24 hours in the electrolytic solution, the aluminium oxide ceramics after then being impregnated using the measurement of identical method was applied
Layer diaphragm.Wherein, the group of electrolyte is divided into 1mol/L LiPF6Solution, solvent are EC:DMC:EMC mass ratio 15:25:60.
Test result shows that the alumina ceramic coating diaphragm of this example preparation, the peel strength before immersion is 35 N/m, electricity
Solving the peel strength after liquid impregnates is 27N/m；The range of decrease under the peel strength of alumina ceramic coating diaphragm before and after electrolyte impregnates
Degree is 22.86%.
Embodiment 2
This example on the basis of embodiment 1, is optimized the dosage of binder；The binder of this example use, oxidation
Aluminium powder, basement membrane, other components of alumina slurry are all same as Example 1, slurry preparation and ceramic-coated separator preparation
Same as Example 1, different is only the dosage of binder, specific as follows:
Test 1: deionized water, alumina powder, binder, dispersing agent, thickener, surfactant are according to weight ratio
70.1:29:0.5:0.1:0.22:0.08 carries out being mixed with alumina slurry；
Test 2: deionized water, alumina powder, binder, dispersing agent, thickener, surfactant are according to weight ratio
69.6:29:1:0.1:0.22:0.08 carries out being mixed with alumina slurry；
Test 3: deionized water, alumina powder, binder, dispersing agent, thickener, surfactant are according to weight ratio
67.6:29:3:0.1:0.22:0.08 carries out being mixed with alumina slurry；
Test 4: deionized water, alumina powder, binder, dispersing agent, thickener, surfactant are according to weight ratio
62.6:29:6:0.1:0.22:0.08 carries out being mixed with alumina slurry；
The alumina slurry tested using above four, prepares four alumina ceramic coating diaphragms respectively, uses
The identical method of embodiment 1 tests the peel strength of four alumina ceramic coating diaphragms；And use 1 phase of embodiment
Same electrolyte and immersion process carries out immersion treatments to four alumina ceramic coating diaphragms respectively, then tests four oxygen
Change the peel strength after aluminium ceramic-coated separator impregnates.
The results show that test 1 alumina ceramic coating diaphragm impregnate front and back peel strength be respectively 34N/m and
25N/m, fall 26%；The peel strength that the alumina ceramic coating diaphragm of test 2 impregnates front and back is respectively 40N/m
And 30N/m, fall 25%；The peel strength that the alumina ceramic coating diaphragm of test 3 impregnates front and back is respectively 70N/
M and 55N/m, fall 22%；Test 4 alumina ceramic coating diaphragm impregnate front and back peel strength be respectively
140N/m and 112N/m, fall 20%.
The above test result shows that, as the dosage of binder increases, alumina ceramic coating diaphragm impregnates the stripping of front and back
Reduce from intensity fall；But with the increase of consumption of binder, on the one hand, it reduces alumina ceramic coating diaphragm
The effect for impregnating the peel strength fall of front and back reaches stable；On the other hand, excessive binder also will affect aluminium oxide
The ceramic characteristics of ceramic coating itself；Therefore, according to the analysis, consumption of binder is preferable in 0.5%-6%.
Comparative example 1
This example prepares alumina ceramic coating diaphragm using the identical material of embodiment 1, the difference is that this example uses
Conventional one-component polyacrylic emulsion replaces the two pack type acrylic bonding agent of documents 1 as binder,
Remaining component, dosage of each component, slurry preparation and ceramic-coated separator preparation are all same as Example 1.This example is equally prepared for applying
Layer is with a thickness of 2 μm, the alumina ceramic coating diaphragm that overall thickness is 16 μm.
It is tested using peel strength of the identical method of embodiment 1 to the alumina ceramic coating diaphragm of this example；And
Immersion treatment is carried out to the alumina ceramic coating diaphragm of this example respectively using the identical electrolyte of embodiment 1 and immersion process,
Then the peel strength after test alumina ceramic coating diaphragm impregnates.
The results show that the peel strength before the alumina ceramic coating diaphragm of this example preparation impregnates is 36N/m, electrolyte
Peel strength after immersion is 18N/m, and peel strength fall is 50%.
Statistically analyze the peel strength before and after the alumina ceramic coating diaphragm immersion electrolyte of embodiment 1 and comparative example 1
Fall, the results are shown in Table 1.
1 alumina ceramic coating diaphragm of table impregnates the peel strength fall before and after electrolyte
Table 1 the results show that compared with comparative example 1, alumina ceramic coating diaphragm prepared by embodiments herein 1,
Fall of its peel strength after impregnating electrolyte may be significantly smaller, and can effectively improve the safety of battery.
The foregoing is a further detailed description of the present application in conjunction with specific implementation manners, and it cannot be said that originally
The specific implementation of application is only limited to these instructions.For those of ordinary skill in the art to which this application belongs, not
Under the premise of being detached from the application design, a number of simple deductions or replacements can also be made.
Claims (10)
1. a kind of electrolyte resistance ceramic-coated separator, the ceramic coating including basement membrane He at least one surface for being coated on basement membrane,
It is characterized by: the ceramic coating is coated with by alumina slurry, the binder used in alumina slurry is polypropylene
Acid or derivatives thereof or polyacrylate or derivatives thereof, with two or more reactive functionalities crosslinking agent,
Cross-linking reaction generates；The reactive functionality is cyanic acid ester group, hydroxyl, carboxyl, epoxy group, amino, sulfydryl, aziridine three-membered ring
At least one of group, carbodiimide groups, ester group and derived functionalized groups of these reactive functionalities.
2. electrolyte resistance ceramic-coated separator according to claim 1, it is characterised in that: the crosslinking agent is epoxy silicon
Alkane, isocyanates, pyridine, aziridines, polycarbodiimide, amino resins and at least one of epoxy group resin.
3. electrolyte resistance ceramic-coated separator according to claim 1, it is characterised in that: in the alumina slurry, glue
Knot agent accounts for the 0.5-8% of alumina slurry total weight；
Preferably, the ratio of binder reactive agent and crosslinking agent is between 100:2-100:30；
Preferably, the ratio of binder reactive agent and crosslinking agent is between 100:5-100:20.
4. electrolyte resistance ceramic-coated separator according to claim 1, it is characterised in that: in the alumina slurry, oxygen
The specific surface area for changing aluminium powder is less than 14m2/ g, the partial size of alumina powder are 0.01 μm≤D50≤10 μm, it is preferred that oxidation
The partial size of aluminium powder is 0.03 μm≤D50≤3 μm.
5. electrolyte resistance ceramic-coated separator according to claim 1, it is characterised in that: the basement membrane with a thickness of 5-20
μm, porosity 30%-60%, aperture is 0.005-0.15 μm；
Preferably, the basement membrane is polyethene microporous membrane, microporous polypropylene membrane or is answered by the multilayer that polyethylene and polypropylene form
Close microporous barrier.
6. electrolyte resistance ceramic-coated separator according to claim 1, it is characterised in that: the ceramic coating with a thickness of
0.5-10μm。
7. electrolyte resistance ceramic-coated separator according to claim 1-6, it is characterised in that: the oxidation aluminium paste
It further include at least one of dispersing agent, thickener and surfactant in material.
8. electrolyte resistance ceramic-coated separator according to claim 7, it is characterised in that: the dispersing agent is polyacrylic acid
At least one of sodium, ammonium polyacrylate, n-butanol, cyclohexanol and ethyl alcohol；
The thickener is at least one of sodium carboxymethylcellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose；
The surfactant is ethylene oxide polymer and/or polyether-based polymers.
9. electrolyte resistance ceramic-coated separator according to claim 8, it is characterised in that: in the alumina slurry, point
Powder accounts for the 0-2% of alumina slurry total weight, and thickener accounts for the 0-5% of alumina slurry total weight, and surfactant accounts for oxygen
Change the 0.05-3% of aluminum slurry total weight.
10. the preparation method of -9 described in any item electrolyte resistance ceramic-coated separators according to claim 1, it is characterised in that:
Include the following steps,
Alumina powder, binder, dispersing agent, thickener and surfactant are mixed in proportion, and are distributed to deionized water
In, it stirs evenly, obtains alumina slurry；
Lithia slurry is applied to at least one surface of basement membrane, drying processing, that is, obtain the ceramic coating every
Film；
Preferably, the coating is specifically using scraper for coating method, Meyer stick rubbing method, reverse roll coating method, intaglio plate roller coating method, leaching
At least one of apply and brush.
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