CN105655523B - A kind of deprotonation dopamine cladding film and the preparation method and application thereof - Google Patents
A kind of deprotonation dopamine cladding film and the preparation method and application thereof Download PDFInfo
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- CN105655523B CN105655523B CN201610196829.2A CN201610196829A CN105655523B CN 105655523 B CN105655523 B CN 105655523B CN 201610196829 A CN201610196829 A CN 201610196829A CN 105655523 B CN105655523 B CN 105655523B
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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 invention discloses a kind of deprotonation dopamines to coat film and the preparation method and application thereof.Its deprotonation dopamine cladding film method be：Auto polymerization is aoxidized in buffer solution be coated on macromolecule membrane matrix surface using DOPA amine monomers, one layer of uniform clad is formed, is impregnated in alkaline solution later, removes cover surface phenolic hydroxyl group, the proton that the functional groups such as carboxyl are contained carries out deprotonation processing.The film that this method is modified not only has impedance low, the high feature of ionic conductivity, more because deprotonation is handled so that battery first charge-discharge efficiency and coulombic efficiency significantly improve, cycle performance enhancing.
Description
Technical field
The present invention relates to battery diaphragm preparation fields, and in particular to a kind of deprotonation dopamine cladding film and its preparation
Method and application.
Background technology
Diaphragm is the important component in lithium battery structure, and performance directly affects the capacity and cycle of corresponding battery
Performance.Main application battery diaphragm is mainly polyolefins film on market today, but in view of homogeneity of product etc.
Problem, the supply of domestic power battery diaphragm are monopolized by external high-end diaphragm manufacturer.Therefore, exploitation has autonomous property right
And the battery diaphragm for possessing excellent properties is very necessary.
Polyolefins film is because of its higher porosity, lower resistance and stronger antiacid alkali ability and good anti-
The advantages such as tearing strength are always the leading role in battery diaphragm market.But it is not strong to the affinity of electrolyte, and very poor is hydrophilic
Property cause its to electrolyte washing lotion/liquid-keeping property it is not strong, to influence the high rate performance in battery charge and discharge process.
A large amount of work, patent CN1554695A have been for the modification people of conventional batteries diaphragm-polyolefins film
It is coated with the copolymer (PVDF-HFP) of one layer of biasfluoroethylene-hexafluoropropylene on polyolefin film surface, passes through PVDF-HFP's
It is highly polar, improve its wellability to electrolyte, document " preparation of novel lithium battery composite diaphragm and its chemical property table
Sign ", on lithium battery diaphragm surface, coating improves wetability of the diaphragm to electrolyte mixed with the polyoxyethylene of nano silicon dioxide
Can, but the active force between the two matrix coat is not strong, the problem of seeing binding force deficiency there are still diaphragm and coating and fall off；
Using other modification processing methods (such as patent CN186077A, CN1476484A) although improving lithium ion battery separator
To the wetting property of electrolyte, but its application and processing cost require height, and there are certain defects.
Dopamine (dopamine) is a kind of biological neural mediator, and under aqueous conditions, it can be in the effect of dissolved oxygen
Lower generation oxidation-cross-linking reaction forms the compound thin layer of poly-dopamine that strength is attached to solid material surface, based on dopamine
This characteristic, membrane technology researchers are epilamellar from poly- compound in solid by dopamine in recent years, and carrying out surface to film changes
Property, and using the poly-dopamine composite layer with reactivity as platform, further surface modification is carried out to film, realize the work(of film
Energyization.
The prior art also discloses that a variety of poly-dopamine modified lithium battery diaphragms.CN103545474A discloses a kind of poly- DOPA
The lithium ion battery separator and preparation method thereof that amine is modified, selections poly-dopamine are active layer, be coated to the surface of diaphragm with
Diaphragm internal control surface, greatly improved the high rate performance of battery；Patent CN103682216A propose it is a kind of utilize biomaterial
The method that dopamine carries out coating modification, dopamine are a kind of chief active object of the stickum of Mussels bio secretion
Matter has matrix strong adsorption capacity, thus can solve the problems, such as coating shedding.But poly-dopamine modified lithium battery every
The battery high rate performance of film is still to be improved.
Invention content
It is modified battery diaphragm for the dopamine of the prior art, in order to further increase the performance of battery multiplying power, inventor
By the way that the study found that the dopamine prepared in the prior art is modified battery diaphragm, the proton contained in dopamine phenolic hydroxyl group can not
The performance to battery avoided has an impact, its cycle performance and coulombic efficiency is caused to decline；By to dopamine coating modification
Polyolefins film carried out deprotonation processing, eliminate the shadow of the proton that is introduced by poly-dopamine coating to battery plus-negative plate
It rings, the cycle performance and high rate performance of corresponding lithium ion battery can be greatly improved.
Specifically, the present invention relates to following technical schemes：
First, the present invention provides a kind of preparation method of the coating modified lithium ion battery separator of dopamine, including walks as follows
Suddenly：
(1) it is bonded with poly-dopamine coating in porous flexible macromolecule membrane matrix surface, prepares the thin of dopamine modification
Film；
(2) dipping by lye is carried out to the film that dopamine is modified, carries out the deprotonation processing of group in poly-dopamine, obtains
It obtains deprotonation dopamine and coats film.
Wherein preferred, the middle flexible macromolecule film as matrix of step (1) is thin for polyethylene film (PE), polypropylene
Film (PP) and polyethylene-polypropylene composite diaphragm (PP-PE), polyethylene terephthalate (PET), polyimides (PI)
Etc. common polyolefins battery diaphragm.
Preferred technical solution, poly-dopamine coating described in step (1) are that DOPA amine monomers aoxidize in buffer solution
Polymerization gained；It is further preferred that poly-dopamine coating layer thickness is 2-100nm.
Preferably, DOPA amine monomers aoxidize auto polymerization in the buffer solution of pH=8.5, wherein the pH conditions of buffer solution
The performance of dopamine composite membrane is played a crucial role, it is most in the prior art it is demonstrated experimentally that dopamine is multiple
It is best to close film autohemagglutination filming performance under the conditions of pH of buffer=8.5, thus, in porous flexible macromolecule membrane table in the present invention
Also the buffer solution of pH=8.5 is used when face is bonded with poly-dopamine coating.
In preferred scheme, lye described in step (2) is one kind of sodium hydroxide, potassium hydroxide or lithium hydroxide solution
Or it is several；Particularly preferred, pH value of solution is between 11-13.
Preferably, the dipping by lye time is 0.5-2h.The homogenieity that dipping by lye processing can influence poly-dopamine coating is (poly-
Dopamine coating can have because of processing to fall off a little), processing time is short, group deprotonation is few in poly-dopamine, therefore, at lye
It is unsuitable too short or long to manage the time.
Preferably, after step (2) dipping by lye, film takes out and is rinsed with deionized water, vacuum or inert gas item
It is dry under part, it obtains deprotonation dopamine and coats film.
In the preparation of deprotonation dopamine cladding film of the present invention, dopamine is prepared using conventional method first and is changed
Property polyolefins film, dopamine are easy in membrane surface auto polymerization into uniform particle sizes under alkalescent buffer conditions, have
The poly-dopamine nano particle of large specific surface area, poly-dopamine coating can be substantially reduced the contact angle of diaphragm and electrolyte,
Electrolyte effectively sprawling in membrane surface is realized, to improve the lyophily performance of diaphragm；Secondly, matter is gone by addition lye
Sub-ization processing, on the one hand, the performance to battery for eliminating the proton contained in poly-dopamine phenolic hydroxyl group in film has an impact shadow
It rings, on the other hand, improves dopamine and coat film to lithium ion permeability, to improve battery first charge-discharge efficiency and library
Human relations efficiency, cycle performance enhancing.
Secondly, technical scheme of the present invention is related to the lithium ion battery separator that above-mentioned preparation method is prepared.
In addition, the present invention also provides the lithium ion batteries for the battery diaphragm being prepared containing above-mentioned preparation method.
Technical solution of the present invention achieves following advantageous effect：
(1) in the modification of battery diaphragm, biomaterial dopamine because its strong adhesive capacity with polarity collection
Group can greatly improve the lyophily ability of existing battery diaphragm and prevent falling off for modified coating, the present invention on this basis,
Deprotonation processing is carried out to coating, the proton contained in itself to reduce dopamine coating bears battery plus-negative plate generation
Face is rung, to further improve the high rate performance of battery；
(2) lithium battery, which relies primarily on lithium ion (positive charge) and moves between a positive electrode and a negative electrode, carrys out work, and the application passes through
Base extraction (pH=11-13), realizing deprotonation dopamine cladding film improves the selective penetrated property of positive charge, lithium
Ion-selective permeability higher, thus, battery first charge-discharge efficiency and coulombic efficiency are further improved, cycle performance of battery
Enhancing.
The present invention provides a kind of application technology of protonation treated the coating modified lithium ion battery separator of dopamine, institute
The dopamine coating that processing must be protonated not only maintains original strong lyophily, more eliminates its dopamine coating institute band itself
There is influence of the proton to battery plus-negative plate, the cycle performance and high rate performance of corresponding lithium ion battery is further improved, not
The battery diaphragm come has wide application prospect in being modified..
Description of the drawings
The coating modified polyethylene film scanning electron microscope diagram of Fig. 1 dopamines
The dopamine modified poly ethylene film scanning electron microscope picture of Fig. 2 deprotonations processing
Fig. 3 PE films, bar amine coating PE films, the high rate performance figure of deprotonation dopamine PE films
Fig. 4 PE films, bar amine coating PE films, the testing impedance performance map of deprotonation dopamine PE films
Specific implementation mode
Embodiment 1
The trishydroxymethylaminomethane (Tris) of 0.9g is taken to be dissolved in mixed solvent (volume 150ml, the body of first alcohol and water first
Product ratio 1:1), then be added dropwise certain density hydrochloric acid to mixed liquor PH be 8.5, later be added 0.3g dopamine hydrochloride, stirring
And it dissolves.Finally, if the pre- washed polyethylene film dry plate of deionized water is immersed mixed liquor for 24 hours.Gained treated diaphragm
It is rinsed repeatedly with deionized water, and is put into dry 6h under the conditions of 60 DEG C of vacuum tank, the as coating modified polyethylene of dopamine is thin
Film.Its scanning electron microscope diagram is as shown in Figure 1, it can be seen that has one layer of uniform dopamine to apply on polyethylene film surface
Layer.
Embodiment 2
Such as 1 the method for embodiment, the coating modified polyethylene film of dopamine is prepared.Prepare the hydroxide of PH=13
Lithium solution, by the coating modified polyethylene film of dopamine, immersion treatment 0.5h, later taking-up are simultaneously rushed with deionized water wherein
It washes repeatedly, dry 6h under the conditions of 60 DEG C of vacuum tank.Its scanning electron microscope diagram is as shown in Figure 2, it is seen that by deprotonation
After processing, dopamine coating has to fall off a little, but entirety still keeps complete.
Embodiment 3
Such as 1 the method for embodiment, the coating modified polypropylene film of dopamine is prepared.Prepare the hydroxide of PH=12
Sodium solution, by the coating modified polypropylene film of dopamine, immersion treatment 1h, later taking-up are simultaneously rinsed with deionized water wherein
Repeatedly, dry 6h under the conditions of 60 DEG C of vacuum tank.
Embodiment 4
Such as 1 the method for embodiment, the coating modified polyethylene-polypropylene laminated film of dopamine is prepared.Prepare PH
=11 potassium hydroxide solution, by the coating modified polyethylene-polypropylene film of dopamine immersion treatment 2h, Zhi Houqu wherein
Go out and rinses multiple, dry 6h under the conditions of 60 DEG C of vacuum tank with deionized water.
Embodiment 5
Such as 1 the method for embodiment, the coating modified polyethylene film of dopamine is prepared.Prepare the hydroxide of PH=13
Lithium solution, by the coating modified polyethylene film of dopamine, immersion treatment 0.5h, later taking-up are simultaneously rushed with deionized water wherein
It washes repeatedly, dry 6h under the conditions of 60 DEG C of vacuum tank.With LiMnO4For anode, graphite is cathode, respectively with polyethylene film, bar amine
Coating modified polyethylene film and the dopamine film of deprotonation processing are battery diaphragm, are assembled into button cell, into
Row high rate performance is tested, and the results are shown in Figure 3, in comparison, its battery of deprotonation treated dopamine modified diaphragm
Charge/discharge capacity and high rate performance it is more preferable.
Embodiment 6
Such as 5 the method for embodiment, to polyethylene film, the coating modified polyethylene film of bar amine and deprotonation
After changing the dopamine film assembling button cell of processing and carrying out high rate performance test, testing impedance is respectively done to it and is compared,
The results are shown in Figure 4.From the results, it was seen that compared to the diaphragm not processed, after the battery system cycle of deprotonation processing
Impedance further decrease.
It should be noted that above example is only used to illustrate the technical scheme of the present invention rather than is limited.Although ginseng
It is described the invention in detail according to given example, but those skilled in the art can be as needed to this hair
Bright technical solution is modified or replaced equivalently, without departing from the spirit of the technical scheme of the invention and range.
Claims (7)
1. a kind of preparation method of the coating modified lithium ion battery separator of dopamine, which is characterized in that
(1) it is bonded with poly-dopamine coating in porous flexible macromolecule membrane matrix surface, prepares the film of dopamine modification；
(2) dipping by lye is carried out to the film that dopamine is modified, carries out the deprotonation processing of group in poly-dopamine, is gone
It protonates dopamine and coats film, wherein lye solution pH is between 11-13；
Poly-dopamine coating described in step (1) is DOPA amine monomers in buffer solution obtained by oxidation polymerization；
The DOPA amine monomers aoxidize auto polymerization in the buffer solution of pH=8.5；
The dipping by lye time is 0.5-2h；
Lye described in the step (2) is the one or more of sodium hydroxide, potassium hydroxide or lithium hydroxide solution.
2. method according to claim 1, which is characterized in that the porous flexible macromolecule membrane as matrix is polyolefins
Film.
3. method according to claim 2, which is characterized in that the polyolefins film is polyethylene film (PE), poly- third
Alkene film (PP) and polyethylene-polypropylene composite diaphragm (PP-PE), polyethylene terephthalate (PET) film or poly-
Acid imide (PI) film.
4. method according to claim 1, which is characterized in that the poly-dopamine coating layer thickness is 2-100nm.
5. method according to claim 1, which is characterized in that after step (2) dipping by lye, film takes out and uses deionization
Water rinses, dry under vacuum or inert gas conditions, obtains deprotonation dopamine and coats film.
6. the lithium ion battery separator being prepared according to any one of claim 1-5 the methods.
7. the lithium ion battery containing battery diaphragm described in claim 6.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610196829.2A CN105655523B (en) | 2016-03-31 | 2016-03-31 | A kind of deprotonation dopamine cladding film and the preparation method and application thereof |
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| CN201610196829.2A CN105655523B (en) | 2016-03-31 | 2016-03-31 | A kind of deprotonation dopamine cladding film and the preparation method and application thereof |
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| CN109786620B (en) * | 2018-12-13 | 2022-03-15 | 武汉中兴创新材料技术有限公司 | Coating film and preparation method and application thereof |
| CN111564639B (en) * | 2020-05-28 | 2023-02-28 | 贝特瑞新材料集团股份有限公司 | Lithium ion battery pole piece, preparation method and application thereof |
| CN112111079B (en) * | 2020-09-24 | 2023-05-16 | 广东省科学院生物工程研究所 | Dopamine-modified polyimide battery diaphragm and preparation method and application thereof |
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| KR20130141234A (en) * | 2012-06-15 | 2013-12-26 | 주식회사 엘지화학 | A separator having porous coating layer and electrochemical device including the same |
| CN103545474A (en) * | 2013-10-29 | 2014-01-29 | 中国第一汽车股份有限公司 | Poly-dopamine modified lithium-ion battery diaphragm and preparation method thereof |
| CN104051695A (en) * | 2014-06-20 | 2014-09-17 | 江苏大学 | Polymer modified diaphragm for lithium sulphur battery, preparation method of polymer modified diaphragm and lithium sulphur battery |
| CN104143614A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Lithium sulfur battery |
| CN104466063A (en) * | 2014-12-09 | 2015-03-25 | 吉林省聚科高新材料有限公司 | Polydopamine surface modified polyether sulfone nanofiber composite diaphragm and preparation method and applications |
| CN105185940A (en) * | 2015-10-23 | 2015-12-23 | 旭成（福建）科技股份有限公司 | Preparation method and application of polyolefin/nanocrystal cellulose composite diaphragm |
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2016
- 2016-03-31 CN CN201610196829.2A patent/CN105655523B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130141234A (en) * | 2012-06-15 | 2013-12-26 | 주식회사 엘지화학 | A separator having porous coating layer and electrochemical device including the same |
| CN104143614A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Lithium sulfur battery |
| CN103545474A (en) * | 2013-10-29 | 2014-01-29 | 中国第一汽车股份有限公司 | Poly-dopamine modified lithium-ion battery diaphragm and preparation method thereof |
| CN104051695A (en) * | 2014-06-20 | 2014-09-17 | 江苏大学 | Polymer modified diaphragm for lithium sulphur battery, preparation method of polymer modified diaphragm and lithium sulphur battery |
| CN104466063A (en) * | 2014-12-09 | 2015-03-25 | 吉林省聚科高新材料有限公司 | Polydopamine surface modified polyether sulfone nanofiber composite diaphragm and preparation method and applications |
| CN105185940A (en) * | 2015-10-23 | 2015-12-23 | 旭成（福建）科技股份有限公司 | Preparation method and application of polyolefin/nanocrystal cellulose composite diaphragm |
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