CN104600232B - A kind of method of modifying of ultra-high molecular mass polyethylene micropore film - Google Patents
A kind of method of modifying of ultra-high molecular mass polyethylene micropore film Download PDFInfo
- Publication number
- CN104600232B CN104600232B CN201510012834.9A CN201510012834A CN104600232B CN 104600232 B CN104600232 B CN 104600232B CN 201510012834 A CN201510012834 A CN 201510012834A CN 104600232 B CN104600232 B CN 104600232B
- Authority
- CN
- China
- Prior art keywords
- ultra
- high molecular
- molecular mass
- micropore film
- mass polyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of method of modifying of ultra-high molecular mass polyethylene micropore film, ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus first；Polymer spray treatment is carried out to the ultra-high molecular mass polyethylene micropore film with the polymer spray coating liquor prepared in advance using the electrostatic spraying apparatus；The amount of the ultra-high molecular mass polyethylene micropore film surface micron particles is controlled by controlling spray time, modified ultra-high molecular mass polyethylene micropore film is obtained.The ultra-high molecular mass polyethylene micropore film being modified by this method has higher porosity, higher charge/discharge capacity and good cycle performance.
Description
Technical field
The present invention relates to technical field of lithium batteries, more particularly to a kind of modification side of ultra-high molecular mass polyethylene micropore film
Method.
Background technology
At present, lithium ion battery is mainly by positive electrode, negative material, electrolyte, barrier film and battery case packaging material
Composition.In lithium ion battery, barrier film has two effects：One is to separate the both positive and negative polarity of battery, prevent the two poles of the earth contact and
Short circuit；Two be to pass through the lithium ion in electrolyte.The performance of barrier film determines the interfacial structure of battery, internal resistance, directly affects
To the capacity, cycle performance and security of battery.
Because ultra-high molecular mass polyethylene micropore film has the ability that very strong external force resistance is punctured, it makes as lithium battery diaphragm
Used time can reduce the short circuit ratio of lithium battery, so as to improve the security of lithium battery.But the superelevation prepared by prior art point
Sub- mass polyethylene micropore film still suffers from that porosity is low, the low problem of charge/discharge capacity.
The content of the invention
It is an object of the invention to provide a kind of method of modifying of ultra-high molecular mass polyethylene micropore film, it is modified by this method
Ultra-high molecular mass polyethylene micropore film have higher porosity, higher charge/discharge capacity and good cycle performance.
A kind of method of modifying of ultra-high molecular mass polyethylene micropore film, methods described includes：
Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus；
It is micro- to the ultra-high molecular weight polyethylene with the polymer spray coating liquor prepared in advance using the electrostatic spraying apparatus
Pore membrane carries out polymer spray treatment；
The amount of the ultra-high molecular mass polyethylene micropore film surface micron particles is controlled by controlling spray time, is obtained
Modified ultra-high molecular mass polyethylene micropore film.
The ultra-high molecular mass polyethylene micropore film is the molecular weight of polyethylene for using thermally induced phase separation to prepare for 800,000
~1,000 ten thousand polyethene microporous membrane.
The polymer spray coating liquor prepared in advance is specifically included：
Specific polymer is dissolved in the polymer spray coating liquor that solvent preparation is obtained, the quality of the polymer spray coating liquor
Concentration is 0.1-15%.
The mass concentration of the polymer spray coating liquor is preferably：3%.
The specific polymer includes：The nanometer obtained by electrostatic spraying of solvent can be dissolved in the height of micron particles
Molecular material.
The specific polymer includes：Kynoar, polypropylene is fine or polypropylene.
Preparing the solvent that the polymer spray coating liquor used includes：Acetone, N,N-dimethylformamide, N, N- dimethyl
Acetamide, one kind in first alcohol and water or any several.
Preparing the solvent that the polymer spray coating liquor used is preferably：By acetone and N,N-dimethylformamide according to 3:
2 mass ratio is formulated.
During polymer spray treatment is carried out to the ultra-high molecular mass polyethylene micropore film：
Spray voltage is 0.1-30kV, and it is 15 ㎝ to receive distance.
The spray voltage is preferably 21kV.
As seen from the above technical solution provided by the invention, the ultra-high molecular weight polyethylene being modified by this method is micro-
Pore membrane has higher porosity, higher charge/discharge capacity and good cycle performance.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, being used required in being described below to embodiment
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is provided the method for modifying schematic flow sheet of ultra-high molecular mass polyethylene micropore film by the embodiment of the present invention；
Fig. 2 is that obtained ultra-high molecular mass polyethylene micropore film putting in lithium battery is modified according to example of the present invention
Capacity curve schematic diagram；
Fig. 3 is that obtained ultra-high molecular mass polyethylene micropore film following in lithium battery is modified according to example of the present invention
Ring stability curve schematic diagram.
Embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
The embodiment of invention, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
The embodiment of the present invention is described in further detail below in conjunction with accompanying drawing, is as shown in Figure 1 present invention implementation
Example provides the method for modifying schematic flow sheet of ultra-high molecular mass polyethylene micropore film, and methods described includes：
Step 11：Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus；
In this step, ultra-high molecular mass polyethylene micropore film is the molecular weight of polyethylene prepared using thermally induced phase separation
For 800,000~10,000,000 polyethene microporous membrane.
Step 12：It is poly- to the super high molecular weight with the polymer spray coating liquor prepared in advance using the electrostatic spraying apparatus
Ethene microporous barrier carries out polymer spray treatment；
In this step, the polymer spray coating liquor prepared in advance is specifically included：
Specific polymer is dissolved in the polymer spray coating liquor that solvent preparation is obtained, the quality of the polymer spray coating liquor
Concentration is 0.1-15%, and preferred mass concentration is 3%.
The specific polymer includes：The nanometer obtained by electrostatic spraying of solvent can be dissolved in the height of micron particles
Molecular material.
In the specific implementation, the polymer can be Kynoar PVDF, polypropylene is fine or the polyphosphazene polymer such as polypropylene
Compound, polymer copolymerization compound.
Prepare the solvent that the polymer spray coating liquor used in addition, above-mentioned and can include：Acetone, N, N- dimethyl formyls
Amine, DMAC N,N' dimethyl acetamide, one kind in first alcohol and water or any several.
Preferred solvent is：By acetone and N,N-dimethylformamide according to 3:2 mass ratio is formulated.
Step 13：The ultra-high molecular mass polyethylene micropore film surface micron particles are controlled by controlling spray time
Amount, obtains modified ultra-high molecular mass polyethylene micropore film.
During polymer spray treatment is carried out to the ultra-high molecular mass polyethylene micropore film：Spray voltage is
0.1-30kV, it is 15 ㎝ to receive distance.
Further, preferably spray voltage is 21kV.
The operation principle of above-mentioned electrostatic spraying apparatus is：According to the physical phenomenon of electrophoresis, using coated article as anode, typically
In the case of be grounded；Coating atomising mechanism is as negative electrode, and negative high voltage of connecting with the mains so is formed high-voltage electrostatic field at the two poles of the earth；
Due to producing corona discharge in negative electrode, ejection paint medium can be made powered, and be further atomized.According to " identical charges repel each other, different in nature phase
Inhale " principle, powered paint medium acted on by electric field force, and the coated article surface of positively charged is directionally flowed to along power line,
Can neutralization precipitation into one layer of uniform, adhesion-tight film.
The preparation method of the present invention is described in detail with reference to instantiation：
Embodiment 1, weighing 0.31gPVDF powder press acetone as polymer, dicyandiamide solution：DMF (N, N- dimethyl formyls
Amine)=3：2 mass ratios are prepared, and obtain the PVDF solution that mass concentration is 3%；
Using solution electrostatic spraying apparatus, spinning voltage 21kV, it is 15 ㎝ to receive distance；Ultra-high molecular weight polyethylene is micro-
Pore membrane is laid on the receiving platform of electrostatic spraying apparatus, is sprayed using the PVDF solution prepared；
Meanwhile, the spray time for controlling PVDF is 2min, and obtained microporous barrier can be as lithium battery diaphragm.
Embodiment 2, weighing 0.31gPVDF powder press acetone as polymer, dicyandiamide solution：DMF (N, N- dimethyl formyls
Amine)=3：2 mass ratios are prepared, and obtain the PVDF solution that mass concentration is 3%；
Using solution electrostatic spraying apparatus, spinning voltage 21kV, it is 15 ㎝ to receive distance；Ultra-high molecular weight polyethylene is micro-
Pore membrane is laid on the receiving platform of electrostatic spraying apparatus, is sprayed using the PVDF solution prepared；
Meanwhile, the spray time for controlling PVDF is 4min, and obtained microporous barrier can be as lithium battery diaphragm.
Embodiment 3, weighing 0.31gPVDF powder press acetone as polymer, dicyandiamide solution：DMF (N, N- dimethyl formyls
Amine)=3：2 mass ratios are prepared, and obtain the PVDF solution that mass concentration is 3%；
Using solution electrostatic spraying apparatus, spinning voltage 21kV, it is 15 ㎝ to receive distance；Ultra-high molecular weight polyethylene is micro-
Pore membrane is laid on the receiving platform of electrostatic spraying apparatus, is sprayed using the PVDF solution prepared；
Meanwhile, the spray time for controlling PVDF is 6min, and obtained microporous barrier can be as lithium battery diaphragm.
It is illustrated in figure 2 and lifts ultra-high molecular mass polyethylene micropore film that the modifications of three examples obtain in lithium according to the present invention
Discharge capacity curve synoptic diagram in battery；It is illustrated in figure 3 stable circulation linearity curve signal of the microporous barrier in lithium battery
Figure, from Fig. 2 and 3：The property of resulting microporous barrier when control PVDF spray time is respectively 2min, 4min and 6min
Energy curve, it is more excellent in terms of discharge capacity and cyclical stability than the performance curve without modified microporous barrier.
In summary, the ultra-high molecular mass polyethylene micropore film that the method provided by the embodiment of the present invention is modified has
The advantages of higher porosity, higher charge/discharge capacity and good cycle performance；High porosity is conducive to lithium ion to exist
Positive and negative interpolar is passed freely through, and the small size aperture of microporous barrier can play a part of isolating both positive and negative polarity, be assembled into after lithium ion battery
Charge/discharge capacity is higher, and cyclical stability is good, improves the cycle performance of lithium battery, service life extension.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art is in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (2)
1. a kind of method of modifying of ultra-high molecular mass polyethylene micropore film, it is characterised in that methods described includes：
Ultra-high molecular mass polyethylene micropore film is laid on the receiving platform of electrostatic spraying apparatus；
Using the electrostatic spraying apparatus with the polymer spray coating liquor prepared in advance to the ultra-high molecular mass polyethylene micropore film
Carry out polymer spray treatment；
The amount of the ultra-high molecular mass polyethylene micropore film surface micron particles is controlled by controlling spray time, is modified
Ultra-high molecular mass polyethylene micropore film afterwards；
Wherein, the polymer spray coating liquor prepared in advance is specifically included：Specific polymer is dissolved in into solvent preparation to obtain
Polymer spray coating liquor, the mass concentration of the polymer spray coating liquor is 0.1-15%；
The specific polymer includes：The nanometer obtained by electrostatic spraying of solvent can be dissolved in the macromolecule of micron particles
Material, is specifically included：Kynoar, polyacrylonitrile or polypropylene；
And prepare the solvent that the polymer spray coating liquor used and include：Acetone and N,N-dimethylformamide are according to 3:2 matter
Amount ratio is formulated；
Further, the mass concentration of the polymer spray coating liquor is specially：3%；
During polymer spray treatment is carried out to the ultra-high molecular mass polyethylene micropore film：
Spray voltage is specially 21kV, and it is 15 ㎝ to receive distance.
2. the method for modifying of ultra-high molecular mass polyethylene micropore film according to claim 1, it is characterised in that
The ultra-high molecular mass polyethylene micropore film is the molecular weight of polyethylene that uses thermally induced phase separation to prepare for 800,000~
10000000 polyethene microporous membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510012834.9A CN104600232B (en) | 2015-01-09 | 2015-01-09 | A kind of method of modifying of ultra-high molecular mass polyethylene micropore film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510012834.9A CN104600232B (en) | 2015-01-09 | 2015-01-09 | A kind of method of modifying of ultra-high molecular mass polyethylene micropore film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104600232A CN104600232A (en) | 2015-05-06 |
| CN104600232B true CN104600232B (en) | 2017-10-24 |
Family
ID=53125869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510012834.9A Expired - Fee Related CN104600232B (en) | 2015-01-09 | 2015-01-09 | A kind of method of modifying of ultra-high molecular mass polyethylene micropore film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104600232B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268356B (en) * | 2015-05-20 | 2021-01-19 | 宁波大学 | Method for preparing ultrahigh molecular weight polyethylene composite hollow fiber by thermally induced phase separation |
| CN105826505A (en) * | 2016-04-16 | 2016-08-03 | 佛山市南海区欣源电子有限公司 | Process for manufacturing diaphragm of wearable flexible battery |
| CN109485884B (en) * | 2018-11-02 | 2021-07-09 | 北京石油化工学院 | Preparation method of polyvinylidene fluoride film |
| CN112259901B (en) * | 2019-07-03 | 2022-03-18 | 比亚迪股份有限公司 | Gluing diaphragm for lithium ion battery and preparation method and application thereof |
| CN110923954A (en) * | 2019-12-19 | 2020-03-27 | 广东工业大学 | High-molecular polymer fiber membrane with through hole structure and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218871B (en) * | 2011-04-14 | 2014-08-27 | 万向电动汽车有限公司 | Preparation method of modified diaphragm for lithium-ion secondary battery as well as product and preparation device thereof |
| CN102299287B (en) * | 2011-08-12 | 2013-05-29 | 沧州明珠塑料股份有限公司 | Composite nanometer fiber lithium ion battery diaphragm and preparation method thereof |
| CN102779964B (en) * | 2012-08-08 | 2015-03-04 | 龙能科技（苏州）有限公司 | Method for preparing multilayer composite membrane for secondary battery by using electrostatic spinning coating method |
| CN103137932A (en) * | 2013-03-04 | 2013-06-05 | 北京石油化工学院 | Microporous polymer isolating film having good wettability on electrolyte and preparation method |
-
2015
- 2015-01-09 CN CN201510012834.9A patent/CN104600232B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104600232A (en) | 2015-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104600232B (en) | A kind of method of modifying of ultra-high molecular mass polyethylene micropore film | |
| CN105261760B (en) | Lithium ion battery aqueous positive-pole composite current collector, positive plate and preparation method thereof, lithium ion battery | |
| CN108886136A (en) | The sulfur electrode and its manufacturing method of multizone | |
| CN108305977A (en) | A kind of caking property polymer-coated lithium ion battery separator and preparation method thereof | |
| WO2020211621A1 (en) | Porous diaphragm and preparation method therefor, and lithium-ion battery | |
| CN108615865A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN103682354A (en) | All-solid-state lithium ion battery composite electrode material and preparation method thereof and all-solid-state lithium ion battery | |
| MY152442A (en) | Process for producing carbon particles for electrode, carbon particles for electrode, and negative-electrode material for lithium-ion secondary battery | |
| CN105576177B (en) | A kind of lithium ion battery reinforced inorganic diaphragm and preparation method thereof | |
| CN109792052A (en) | Lithium-sulfur rechargeable battery anode acrylic adhesives and application thereof | |
| CN112127011B (en) | Polyacrylonitrile/cellulose composite fiber membrane and preparation method and application thereof | |
| CN104466063A (en) | Polydopamine surface modified polyether sulfone nanofiber composite diaphragm and preparation method and applications | |
| CN114050260B (en) | Positive electrode film layer additive composition, positive electrode film layer additive, positive electrode plate and secondary battery | |
| CN103094513B (en) | Lithium ion battery film in situ preparation method, lithium ion battery film, and lithium ion battery | |
| CN103746087A (en) | Method for manufacturing lithium-ion battery separators and lithium battery | |
| CN107591561A (en) | A kind of preparation method of lithium ion battery gel polymer electrolyte | |
| CN113690418A (en) | Modified active material for semi-solid battery and preparation method and application thereof | |
| CN104319361A (en) | Method for preparing composite diaphragm | |
| CN112909322B (en) | In-situ formed sulfide composite solid electrolyte and preparation method thereof | |
| KR101742881B1 (en) | The coating composition contained ionic inorganic particles and membrane for redox flow battery using the same | |
| CN109411762A (en) | A kind of utter misery aluminium foil and preparation method thereof | |
| KR20220018049A (en) | Adhesive-coated separator for lithium ion battery, method for preparing same, and use thereof | |
| CN105870382B (en) | Lithium ion battery composite diaphragm and preparation method thereof | |
| CN104505553B (en) | A kind of lead-acid accumulator regenerated liquid concentrated solution and preparation method thereof | |
| WO2017054297A1 (en) | Electrode for electrochemical power supply and manufacturing method therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171024 Termination date: 20210109 |