CN101735470B - Method for preparing lithium ion battery membrane via radiation grafting modification by using polypropylene film - Google Patents
Method for preparing lithium ion battery membrane via radiation grafting modification by using polypropylene film Download PDFInfo
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- CN101735470B CN101735470B CN2009101995340A CN200910199534A CN101735470B CN 101735470 B CN101735470 B CN 101735470B CN 2009101995340 A CN2009101995340 A CN 2009101995340A CN 200910199534 A CN200910199534 A CN 200910199534A CN 101735470 B CN101735470 B CN 101735470B
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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
Abstract
The present invention relates to a method for preparing lithium ion battery membrane via radiation grafting modification by using a polypropylene film, belonging to the technical field of high polymer material modification. The method comprises the main processes of: (1) preparing a grafting reaction reagent system and using methacrylic acid shrinkage glyceride with the volume ratio of 15 percent, solvent N,N-dimethylformamide with the volume ratio of 85 percent and a proper amount of inhibitor ammonium ferrous sulfate to form the reagent system; (2) placing a polypropylene film to be processed in a polyethylene bag, filling with nitrogen and placing in an electron irradiation room after being sealed for irradiation, wherein the electron beam intensity is 2mA and the irradiation dose is 100kGy; and (3) placing the irradiated polypropylene film in the mixed solution of the reaction reagent system, performing grafting reaction for 2 hours under the condition of constant-temperature water bath at 50 DEG C, washing and drying to obtain the polypropylene battery membrane via grafting modification. The membrane has favorable electrochemistry property via constant-current charging and discharging test in the lithium ion battery.
Description
Technical field
The present invention relates to a kind of method of utilizing the polypropylene film via radiation grafting modification to prepare lithium ion battery separator, belong to the polymer modification technical field.
Background technology
By the microporous membrane (polyethylene, polypropylene, perhaps both matrix materials) of polyolefin prepared by widely as lithium battery diaphragm.Though polyolefin film shows good electrochemical stability in lithium cell, because their intrinsic hydrophobicity causes them to be difficult to be soaked fully by electrolyte solution.Therefore, the modification of carrying out polyolefin film improves its affinity to electrolyte solution and is necessary.The modification of this polyolefin film can comprise that physics and chemical means realize by the utilization diverse ways.Functional groups such as ester group are grafted to improve its absorption and liquid-keeping property on the polypropylene film to a great extent, and improve the ionic conductivity of lithium cell electrolyte solution.
Summary of the invention
The objective of the invention is to utilize the electron beam irradiation crosslinking technology to prepare lithium ion battery separator, a kind of method of utilizing the polypropylene film via radiation grafting modification to prepare lithium ion battery separator is provided.
A kind of method of utilizing the polypropylene film via radiation grafting modification to prepare lithium ion battery separator of the present invention is characterized in that having following process and step:
A. at first prepare the graft reaction reagent system, main agents composition and volumn concentration are in this system:
Glycidyl methacrylate (being called for short GMA) 15%;
N, dinethylformamide (being called for short DMF) 85%;
Above-mentioned DMF is molten for reaction; Add the stopper ferrous ammonium sulphate in addition, its add-on is a benchmark with mentioned reagent GMA and DMF weight summation 100, and getting its weight percent is 0.02%;
B. polypropylene film is used the acetone scrub, and dried, the polypropylene film after weighing is put into polyethylene bag, and in bag, charge into high pure nitrogen, after sealing, place the electron irradiation chamber to carry out irradiation to drive wherein air away to constant weight; The electron beam that irradiation adopted can be 1.8MeV; Electronic beam current intensity is 2mA, and irradiation dose is 100kGy; Be positioned over then in the refrigerator, standby;
C. the polypropylene film behind the irradiation is rolled up on glass stick, be placed on after tying and fill above-mentioned monomer glycidyl methacrylate (GMA) and solvent N, in the grafting container of dinethylformamide (DMF) and stopper ferrous ammonium sulphate; Fill high pure nitrogen, after the sealing grafting container is positioned in 50 ℃ the constant temperature water bath; Behind the graft reaction 2 hours, the polypropylene film after the grafting is taken out, use N, dinethylformamide (DMF) washing was then soaked wherein 8 hours again, to remove the film surface homopolymer; It is dry down to put into 50 ℃ in baking oven then, finally obtains the polypropylene battery diaphragm of graft modification.
Characteristics of the present invention and advantage are as described below:
The inventive method is utilized the pre-irradiation grafting technology, and adopt the accelerator electron beam to cause mode and on the polypropylene film matrix, produce the free radical activity site that can be used for the initiation grafting reaction, thus monomer-grafted to these active sites GMA.
The inventive method can change monomeric percentage of grafting flexibly by control graft reaction time, monomer concentration and stopper consumption, thereby regulates the introducing amount of ester group on the grafted chain.
The inventive method directly is matrix with the polypropylene film, causes by means of electron beam irradiation and carries out graft reaction, and easy to operate, cost is also lower.
The inventive method synthesizing lithium ion battery barrier film possesses imbibition, liquid-keeping property is strong, good characteristics such as ionic conductivity height.
Description of drawings
Fig. 1 carries out charge and discharge cycles voltage-capacity relationship graphic representation 30 times for the polypropylene grafted film of the present invention.(the film percentage of grafting is 63.64%)
Fig. 2 is cell container and charge and discharge cycles number of times corresponding relation graphic representation among the present invention.Wherein: (a) percentage of grafting 63.64%, and (b) percentage of grafting 125.45%, (c) graft copolymer membrane not.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Preparation process among the embodiment and step are not as follows:
(1) at first dose volume than GMA: DMF=15: 85 graft reaction solution; Add ferrous ammonium sulphate 0.02wt% in addition;
(2) then with polypropylene screen with the acetone scrub and dry to constant weight, the film after weighing is put into polythene film bag, and in bag, charges into high pure nitrogen and carry out irradiation in the electron irradiation chamber to drive wherein air away, to seal to be placed on; Electronic beam current intensity is 2mA, and total irradiation dose is 100kGy;
(3) film behind the irradiation is rolled up on glass stick, tie and be placed in the grafting pipe that fills GMA and DMF, after the inflated with nitrogen sealing grafting pipe is placed 50 ℃ of thermostat(t)ed water fluid bowls, behind the graft reaction 2 hours, graft copolymer membrane is taken out from the grafting pipe, with the DMF washing, then soaked 8 hours earlier, to remove film surface homopolymer with DMF; It is dry down to put into 50 ℃ in baking oven then, finally obtains the polypropylene battery diaphragm of graft modification.
The polypropylene grafted battery diaphragm that embodiment makes discharges and recharges test in lithium ion battery
Polypropylene grafted film is assembled in experiment carries out constant current charge and discharge test in the lithium ion battery.Concrete grammar is: in purifying glove box, the PP film after the graft modification is cut into desired size, be compounded on the positive plate that scribbles a small amount of electrolytic solution, colding pressing by alternate positive and negative with the close negative plate of size then is compound to, and forms the battery base substrate.Under ar gas environment, in 22～24 ℃ the constant temperature, left standstill 10 hours.Carry out loop test subsequently, the charge and discharge cycles test is finished on BT-3043 type cell tester.Charge and discharge mode is a constant current mode, and electric current is set to 1mA, and all circulations are measured and all finished under room temperature (22～24 ℃).Sample battery charge stopping potential is 4.2V, and discharge cut-off voltage is 2.5V.
Test-results, referring to Fig. 1, from cyclic curve shown in Figure 1 as can be seen, after going through 30 constant current charge-discharge circulations, charging and discharging curve has goodish repeatability, this shows that experiment lithium ion battery electric weight after charge and discharge cycles repeatedly substantially still keeps constant, has further confirmed that the lithium ion battery separator of radiation modification method preparation has excellent chemical property simultaneously.
In the above-mentioned experiment lithium ion battery, the electrolytic solution of employing is the LiPF of 1mol/L
6+ EC/DE/DMC, just very LiCoO
2, negative pole is the modified natural graphite material.Charge and discharge mode is a constant current mode, and electric current is set to 1mA.
The modified polypropene film of different percentage of grafting and the comparison test of unmodified polypropylene screen are as described below:
The modified membrane of different percentage of grafting and unmodified polypropylene film be assembled in respectively carry out constant current charge and discharge test in the experiment lithium ion battery.Investigate percentage of grafting to diaphragm electrochemical Effect on Performance rule.The result is referring to Fig. 2, and as can be seen from Figure 2, percentage of grafting is that obviously to be better than percentage of grafting be 125.45% film and graft copolymer membrane not to the circulation volume performance of 63.64% film.The utilization percentage of grafting is that the battery of 63.64% film assembling not only has good circulation volume preserving property, and discharges and recharges coulombic efficiency and keep a high level always.Therefore, we may reach a conclusion, and are suitable as the barrier film of chargeable lithium ion battery after the PP graft modification, and in the percentage of grafting scope that is fit to, graft copolymer membrane can have better electrochemical performance.
Claims (1)
1. method of utilizing the polypropylene film via radiation grafting modification to prepare lithium ion battery separator is characterized in that having following process and step:
A. at first prepare the graft reaction reagent system, main agents composition and volumn concentration are in this system:
Glycidyl methacrylate (being called for short GMA) 15%;
N, dinethylformamide (being called for short DMF) 85%;
Above-mentioned DMF is a reaction solvent; Add the stopper ferrous ammonium sulphate in addition, its add-on is a benchmark with mentioned reagent GMA and DMF weight summation 100, and getting its weight percent is 0.02%;
B. polypropylene film is used the acetone scrub, and dried, the polypropylene film after weighing is put into polyethylene bag, and in bag, fill high pure nitrogen, after sealing, place the electron irradiation chamber to carry out irradiation to drive wherein air away to constant weight; The electron beam that irradiation adopted can be 1.8MeV; Electronic beam current intensity is 2mA, and irradiation dose is 100kGy; Be positioned over then in the refrigerator, standby;
C. the polypropylene film behind the irradiation is rolled up on glass stick, be placed on after tying and fill above-mentioned monomer glycidyl methacrylate (GMA) and solvent N, in the grafting container of dinethylformamide (DMF) and stopper ferrous ammonium sulphate, seal after charging into high pure nitrogen; The grafting container is positioned in 50 ℃ the constant temperature water bath; Behind the graft reaction 2 hours, the polypropylene film after the grafting is taken out, use N, dinethylformamide (DMF) washing was then soaked wherein 8 hours again, to remove the film surface homopolymer; It is dry down to put into 50 ℃ in baking oven then, finally obtains the polypropylene battery diaphragm of graft modification.
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| CN2009101995340A CN101735470B (en) | 2009-11-26 | 2009-11-26 | Method for preparing lithium ion battery membrane via radiation grafting modification by using polypropylene film |
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| CN101735470B true CN101735470B (en) | 2011-11-23 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108635B (en) * | 2011-01-25 | 2012-05-09 | 桂林正翰科技开发有限责任公司 | Method for preparing battery diaphragm material by irradiation grafting of acrylic acid |
| CN102163704B (en) * | 2011-03-24 | 2013-08-28 | 中山国安火炬科技发展有限公司 | Lithium battery diaphragm and production method thereof |
| CN103421208B (en) * | 2013-05-23 | 2015-04-29 | 浙江大学 | Irradiation cross-linking lithium-ion battery diaphragm and preparation method thereof |
| CN103524774B (en) * | 2013-09-22 | 2015-09-16 | 佛山市金辉高科光电材料有限公司 | The method of high performance lithium ion battery barrier film is prepared in a kind of vacuum ultraviolet (VUV) graft modification |
| CN104241571A (en) * | 2014-09-16 | 2014-12-24 | 中国科学院化学研究所 | Hydrophilic lithium ion battery membrane |
| CN105206775B (en) * | 2015-09-11 | 2017-10-17 | 湖南中锂新材料有限公司 | A kind of method that polyethylene surface grafting polyethylene glycol adipate prepares lithium battery diaphragm |
| CN112133871A (en) * | 2020-09-24 | 2020-12-25 | 湖南省凯纳方科技有限公司 | Surface grafting method of mh-ni battery diaphragm |
| CN113904058B (en) * | 2021-10-09 | 2023-08-29 | 远景动力技术(江苏)有限公司 | Separator, method for producing the same and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4339473A (en) * | 1980-08-28 | 1982-07-13 | Rai Research Corporation | Gamma radiation grafting process for preparing separator membranes for electrochemical cells |
| CN1970605A (en) * | 2006-11-09 | 2007-05-30 | 上海大学 | Method for preparing polyethylene ion chelating membrane by radiation graft method |
| CN101519501A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for preparing polypropylene ion chelating membrane by radiation grafting method |
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2009
- 2009-11-26 CN CN2009101995340A patent/CN101735470B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4339473A (en) * | 1980-08-28 | 1982-07-13 | Rai Research Corporation | Gamma radiation grafting process for preparing separator membranes for electrochemical cells |
| CN1970605A (en) * | 2006-11-09 | 2007-05-30 | 上海大学 | Method for preparing polyethylene ion chelating membrane by radiation graft method |
| CN101519501A (en) * | 2009-02-24 | 2009-09-02 | 上海大学 | Method for preparing polypropylene ion chelating membrane by radiation grafting method |
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