CN1710732A - Cell diaphragm, its preparation method and zinc electrode secondary battery containing said diaphragm - Google Patents
Cell diaphragm, its preparation method and zinc electrode secondary battery containing said diaphragm Download PDFInfo
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- CN1710732A CN1710732A CNA2004100251769A CN200410025176A CN1710732A CN 1710732 A CN1710732 A CN 1710732A CN A2004100251769 A CNA2004100251769 A CN A2004100251769A CN 200410025176 A CN200410025176 A CN 200410025176A CN 1710732 A CN1710732 A CN 1710732A
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- barrier film
- zinc
- diaphragm
- base material
- film
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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 disclosed diaphragm includes basis material of polymer microporous membrane, and one or more materials selected from C2 - C10 olefinic bond unsaturated monomers, or monomer of polyethenoxy ether oligomer containing phenolic, alkyl group with polymerization degree lower than 100 grafted on the microporous membrane. Grafting ratio of basis material of polymer microporous membrane is 10 - 80%, and resistance is 0.01 - 0.15 omega.cm2. The disclosed method includes steps: (1) preparing solution of containing one or more grafted monomer; (2) irradiation grafting is carried out for basis material of polymer microporous membrane in prepared solution so as to obtain diaphragm; irradiation dose is 1Kgry - 20Kgry; (3) drying grafted diaphragm. The disclosed diaphragm is applicable to secondary battery of zinc electrode such as nickel zinc cell, zinc silver oxide cell, zinc air cell etc, and suitable to nickel zinc cell especially.
Description
Technical field
The present invention relates to a kind of barrier film that is used for the zinc electrode secondary cell and preparation method thereof, and relate to the secondary cell that makes with this barrier film.
Background technology
The zinc electrode secondary cell is widely used in fields such as electronic device, video equipment and electric motor car.This battery adopts zinc as battery electrode material, compares with traditional cadmium nickel, lead-acid battery, not only has electrical property preferably, and environmentally safe.Zinc electrode secondary cell, especially zinc-nickel cell as one of candidate target of electric car power supply, have the advantage that other similar batteries such as specific energy height, safety and environmental protection can not be compared.U.S. ElectroChem has formulated the target of zinc-nickel cell as the startup lighting point ignition source of portable electric tool power supply and minibus, van, and long-range planning will be as the electrical source of power of electric automobile.
But zinc electrode exists problems such as distortion, dendrite, corrosion and passivation, causes the zinc electrode secondary cell to have defectives such as cycle life is short, self discharge is serious, the circulation volume decline is fast.
An approach eliminating or improve above-mentioned defective fully is that the barrier film to this battery improves.Barrier film can reduce self-discharge of battery, stops dendrite short circuit, delay inducing capacity fading as the cardiac component of secondary zinc battery, thereby improves the cycle life and the performance of battery.Therefore, the quality of zinc electrode secondary battery membrane and performance will be directly connected to the high performance of zinc electrode secondary cell and apply.
The Andre H.Bull.Soc.Fr.Electricians that first phase nineteen forty-one publishes discloses a kind of glassine paper diaphragm material.Though this cellophane material can be obtained good effect, glassine paper is less stable and easy oxidized degraded in alkaline solution.
Study more diaphragm material in recent decades and mainly contain two big classes: microporous barrier and microporous compound film.United States Patent (USP) 4,652,504 disclose a kind of barrier film that disperses passage and a large amount of projection particles that has.It is reported that this film can loose the zinc ion flow point to reach and delay the purpose that zinc dendrite pierces through barrier film by projection particle and dispersion passage, thereby has prolonged the useful life of barrier film.The shortcoming of this film is the manufacturing process complexity, to the precision requirement height of technology.
United States Patent (USP) 4,279,979 disclose a kind of polyolefin fento and polyamide fento blend heat bonding nonwoven fabrics and the compound barrier film of perforated membrane.This patent is described the method for making non-woven fabrics base material in detail, but does not have about the application example of this composite membrane in the zinc electrode secondary cell in the article.
United States Patent (USP) 4,279,978 have introduced a kind of barrier film that contains polyamide, hydrophilic polymer and packing material.It is reported that the packing material in this barrier film can react with metallic zinc and reach the purpose of eliminating zinc dendrite, thereby has prolonged the useful life of barrier film.The packing material that uses in the patent is metal oxide, and it is the fatal shortcoming of this barrier film that metal oxide comes off from barrier film in the use of barrier film.
United States Patent (USP) 4,192,908 have introduced and have a kind ofly had composite membrane than the lower hydrogen potential material of zinc electrode at microporous barrier surface coated one deck.It is reported that the low hydrogen potential material in the coating of this barrier film can react with metallic zinc and reach the purpose of eliminating zinc dendrite, thereby has prolonged the useful life of barrier film.This barrier film in use needs to be clipped in the two-layer microporous polyolefin film, and reaction produced hydrogen, and these development for sealing zinc electrode secondary cell are disadvantageous.
Therefore, need a kind ofly can delay or stop the zinc dendrite growth to pierce through effectively, preparation technology be easy, and stable performance in use helps making the barrier film that seals the zinc electrode secondary cell.
The content of invention
The invention provides a kind of barrier film, it comprises the polymer micro film base material and is grafted on this microporous barrier one or more and is selected from C
2～C
10The ethylene linkage unsaturated monomer, or the degree of polymerization that contains phenolic group, alkyl is less than the monomer of 100 APEO oligomer.The percent grafting of described polymer micro film base material is 10-80%, and the resistance of described barrier film is 0.01～0.15 Ω cm
2, be 80～400% by its liquid absorption of weight of barrier film.
The present invention also provides the preparation method of described barrier film, and it comprises the steps:
A) preparation contains the solution of one or more grafted monomers.
B) the polymer micro film base material is carried out irradiation grafting in described solution, make barrier film, irradiation dose is 1KGry～20KGry.
C) dry barrier film through grafting.
Further aspect of the present invention provides a kind of zinc electrode secondary cell that contains barrier film of the present invention.
Embodiment
The invention provides a kind of preparation method who is used for the barrier film of zinc electrode secondary cell, it comprises the steps:
A) preparation contains the solution of one or more grafted monomers;
B) the polymer micro film base material is carried out irradiation grafting in described solution, make barrier film;
C) dry described barrier film.
A) preparation contains the solution of one or more grafted monomers
In the methods of the invention, at first prepare the solution that contains one or more grafted monomers.Can select suitable grafted monomers according to concrete needs.For example, grafted monomers of the present invention can be selected from C
2～C
10The ethylene linkage unsaturated monomer, or the degree of polymerization that contains phenolic group, alkyl is less than 100 APEO oligomer.
Described C
2-C
10The indefiniteness example of ethylene linkage unsaturated monomer acrylic monomer is arranged, for example acrylic acid, (methyl) acrylic acid, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate.
The described degree of polymerization that contains phenolic group, alkyl has OPEO, NPE less than the indefiniteness example of 100 APEO oligomer.
According to the requirement to the barrier film that forms, grafted monomers of the present invention can use separately, and perhaps two or more are used in combination.
The solvent that is used to prepare described grafted monomers solution is without particular limitation, as long as it does not influence irradiation grafting.At one preferably in the example of the present invention, described solvent is a water.
The concentration of described grafted monomers in solution depends on concrete barrier film requirement.In a better example of the present invention, the concentration of grafted monomers solution is 1-20 weight %, is preferably 5-10 weight %.In example of the present invention, using main component (OPEO) content is the solution graft copolymerization microporous polypropylene membrane of 5 weight %; Using main component (acrylic acid) content in another instantiation of the present invention is the solution graft copolymerization polyethene microporous membrane of 15 weight %.
B) the polymer micro film base material is carried out irradiation grafting in described solution, make barrier film;
Be applicable to that polymer micro film base material of the present invention is a polymer micro film base material known in the art, concrete polymer micro film base material depends on the requirement to barrier film.
The indefiniteness example of described polymer microporous film has, for example microporous polypropylene membrane, polyethene microporous membrane, polyolefin copolymer microporous barrier.This microporous barrier is commercially available, for example, and available from the polyethene microporous membrane of the purple Jiang Jituan in Shanghai.
Be applicable to the porosity normally 20～80% of the polymer micro film base material of barrier film of the present invention, longitudinal fracture intensity is not less than 0.5Kg/1.5cm, and micropore size is at 0.2～10 mu m range.
Before irradiation grafting, better described membrane for polymer is carried out pre-treatment, to remove the impurity and the inorganic matter of deentrainment.Described pre-treating method is well-known in the art, for example, can adopt methods such as pickling, washing.
Place the monomer solution that makes above to carry out irradiation grafting this polymer micro film base material subsequently.Irradiation dose scope 1～20KGry is preferably 3-15KGry, more preferably 5-10KGry.
Irradiation generally carried out 1-7 hour, better carried out 3-5 hour, depended on the power of radiation source.In a better example of the present invention, the dose rate scope of irradiation is 1～100KGry/h, is preferably 10-80KGry/h, more preferably 30-50KGry/h.
The radiation source that is used for irradiation grafting barrier film of the present invention is without particular limitation.In a better example of the present invention, described radiation source is
60Co.
C) dry described barrier film
Take out the barrier film that makes after irradiation is finished and carry out drying.The drying means that adopts can be any method known in the art.In a better example of the present invention, the barrier film that makes is carried out the air drying.
Another aspect of the present invention provides a kind of barrier film that is made by the inventive method, and it comprises the polymer micro film base material and be grafted on this microporous barrier one or more and is selected from C
2～C
10The ethylene linkage unsaturated monomer or the degree of polymerization that contains phenolic group, alkyl are less than 100 APEO oligomer, and the percent grafting of described polymer micro film base material is 10-80%, and the resistance of described barrier film is 0.01～0.15 Ω cm
2, by barrier film weight, its liquid absorption is 80～400%.
The polymer micro film base material that is applicable to barrier film of the present invention is the polymer microporous film of this area routine, and the indefiniteness example of this polymer microporous film has, for example microporous polypropylene membrane, polyethene microporous membrane, polyolefin copolymer microporous barrier.This microporous barrier is commercially available, for example, and available from the polyethene microporous membrane of the purple Jiang Jituan in Shanghai.
Be applicable to the porosity normally 20～80% of the polymer micro film base material of barrier film of the present invention, longitudinal fracture intensity is not less than 0.5Kg/1.5cm, and micropore size is at 0.2～10 mu m range.
The monomer that is used for the described polymer micro film base material of grafting can be selected from C
2～C
10The ethylene linkage unsaturated monomer, the degree of polymerization that contains phenolic group, alkyl is less than 100 APEO oligomer.
Described C
2-C
10The indefiniteness example of ethylene linkage unsaturated monomer acrylic monomer is arranged, for example acrylic acid, (methyl) acrylic acid, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate.
The described degree of polymerization that contains phenolic group, alkyl has OPEO, NPE less than the indefiniteness example of 100 APEO oligomer.
In barrier film of the present invention, the percent grafting of described polymer micro film base material is 10-80%, is preferably 20-60%, more preferably 30-50%; The resistance of final barrier film is 0.01～0.15 Ω cm
2, be preferably 0.03～0.12 Ω cm
2, be preferably 0.04～0.10 Ω cm
2By the weight of barrier film, its liquid absorption is 80～400%, is preferably 100～300%, is preferably 110～200%.
The battery diaphragm that obtains among the present invention can be used for zinc electrode secondary cell such as zinc-nickel cell, zinc-silver oxide cell, zinc-bromine bettery, zinc-air cell etc., is particularly useful for zinc-nickel cell.
Barrier film of the present invention has the following advantages:
1. absorbency and guarantor's fluidity are good, have low resistance;
2. have certain intensity, be difficult for being penetrated by zinc dendrite;
3. anti-alkali corrosion is good;
4. have certain gas-premeable, help the smooth migration of gas;
5. reduce the self discharge of zinc negative pole effectively and in battery charge and discharge process, delayed capacity attenuation.
Further specify the present invention below in conjunction with embodiment.
Embodiment
Method of testing
1. electric performance test
The resistance of barrier film adopts the test of Low ESR resistance meter, and test adopts the KOH solution of 30% mass percent as electrolyte, and test adopts argent as pole plate, and probe temperature is 22～25 ℃.
2. hydrophilicity test
The liquid absorption computing formula of barrier film is:
Test adopts the KOH solution of 30% mass percent as barrier film absorbent solution, in room temperature the barrier film through weighing is soaked 24 hours in barrier film absorbent solution, and taking-up drains, weigh, with above-mentioned formula calculate the liquid absorption of barrier film.
3. assembling cell test
Assemble the zinc-nickel cell with the barrier film that the embodiment of the invention makes.The charge-discharge performance of cell (comprising battery initial capacity and cycle life etc.) adopts charging/discharging of secondary cell performance testing apparatus (BT-2000 alkaline battery test macro is available from U.S. Arbin Instr Ltd.) test.The cell depth of discharge adopts 100DOD.
Embodiment 1
Present embodiment explanation irradiation dose is to the influence of the barrier film that finally makes.
Is in the grafting liquid of 10 weight % (solvent is a water) behind the listed dosage of irradiation such as following table 1 with the microporous polypropylene membrane base material at main component OPEO content, take out, and drying obtains barrier film after overpickling.According to the electrical property of testing standard test barrier film, hydrophilicity the results are shown in following table 1.
Table 1
Test result shows that irradiation dose is in 1～20KGry scope, and the resistance of barrier film is lower than 0.15 Ω cm
2, liquid absorption is greater than 100%.
Embodiment 2
The situation of the barrier film that present embodiment explanation variable concentrations grafting liquid makes.
The microporous polypropylene membrane base material in the grafting liquid of the main component NPE mass percentage content listed as following table 2 behind (solvent is a water) irradiation same dose (10KGry), and is obtained barrier film through washing back drying.According to the electrical property of testing standard test barrier film, hydrophilicity the results are shown in following table 2.
Table 2
Test result shows that grafted monomers concentration is (percentage by weight) in 2～20% scopes, and the resistance of barrier film is lower than 0.15 Ω cm
2, liquid absorption is greater than 100%.
Embodiment 3
The operating position of barrier film in zinc-nickel cell that makes among present embodiment explanation the present invention.
The following barrier film that makes:
Adopt microporous polypropylene membrane as base material, main component NPE content is 5 weight % in the grafting liquid, irradiation dose 10KGry.Microporous barrier irradiation after after the overpickling drying obtain barrier film.
The barrier film that makes above is assembled in the zinc-nickel cell of 30Ah and 40Ah, test battery initial capacity and cycle life the results are shown in following table 3.The end-of-life line is 80% of a rated capacity.
Table 3
Test result shows that the battery initial capacity is normal, and cycle life is greater than 350 times.
Embodiment 4
Present embodiment illustrates the influence of different grafted monomers to the final barrier film that makes.
The microporous polypropylene membrane base material in the listed grafted monomers (solvent is a water) of following table 4 behind the irradiation dose 10KGry, is taken out that drying obtains barrier film after overpickling.According to the electrical property of testing standard test barrier film, hydrophilicity the results are shown in following table 4.
Table 4
Test result shows that electrical property and hydrophilicity all can reach the requirement among the present invention after the base material grafting different monomers.
Embodiment 5
Present embodiment explanation different substrate materials is to the influence of the final barrier film that makes.
The microporous barrier base material that following table 5 is listed takes out that drying obtains barrier film after overpickling in the grafting liquid of main component acrylic acid content 15 weight % (solvent is a water) behind the irradiation dose 10KGry.According to the electrical property of testing standard test barrier film, hydrophilicity the results are shown in following table 5.
Table 4
Test result shows that electrical property and hydrophilicity all can reach the requirement among the present invention after different substrate materials was handled through the grafting among the present invention.
Claims (10)
1. barrier film, it comprises the polymer micro film base material and is grafted on this microporous barrier one or more and is selected from C
2～C
10The ethylene linkage unsaturated monomer, or the degree of polymerization that contains phenolic group, alkyl is less than the monomer of 100 APEO oligomer, the percent grafting of described polymer micro film base material is 10-80%, resistance is 0.01～0.15 Ω cm
2
2. barrier film as claimed in claim 1 is characterized in that its liquid absorption of weight by barrier film is 80～400%, and resistance is 0.03-0.12 Ω cm
2
3. barrier film as claimed in claim 2 is characterized in that its liquid absorption of weight by barrier film is 110～200%, and resistance is 0.04-0.10 Ω cm
2
4. as any one described barrier film among the claim 1-3, it is characterized in that described C
2-C
10The ethylene linkage unsaturated monomer be selected from (methyl) acrylic acid, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate; The described degree of polymerization that contains phenolic group, alkyl is selected from OPEO or NPE less than 100 APEO oligomer.
5. as any one described barrier film among the claim 1-3, the porosity that it is characterized in that the polymer micro film base material is 20%～80%, and longitudinal fracture intensity is not less than 0.5Kg/1.5cm, and micropore size is at 0.2 μ m～10 mu m ranges.
6. the preparation method of barrier film according to claim 1, it comprises the steps:
A) preparation contains the solution of one or more grafted monomers;
B) the polymer micro film base material is carried out irradiation grafting in described solution, make barrier film, irradiation dose is 1KGry～20KGry;
D) dry barrier film through grafting.
7. method as claimed in claim 6 is characterized in that described irradiation dose is 3-15kGry.
8. method as claimed in claim 7 is characterized in that described irradiation dose is 5-10kGry.
9. as any one described method among the claim 6-8, the concentration that it is characterized in that grafted monomers solution is 1-20 weight %.
10. one kind contains the zinc electrode secondary cell that right requires 1 described barrier film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100251769A CN100452485C (en) | 2004-06-16 | 2004-06-16 | Cell diaphragm, its preparation method and zinc electrode secondary battery containing said diaphragm |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100251769A CN100452485C (en) | 2004-06-16 | 2004-06-16 | Cell diaphragm, its preparation method and zinc electrode secondary battery containing said diaphragm |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1710732A true CN1710732A (en) | 2005-12-21 |
| CN100452485C CN100452485C (en) | 2009-01-14 |
Family
ID=35706935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100251769A Expired - Fee Related CN100452485C (en) | 2004-06-16 | 2004-06-16 | Cell diaphragm, its preparation method and zinc electrode secondary battery containing said diaphragm |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728505B (en) * | 2009-12-18 | 2013-04-03 | 河南科高辐射化工科技有限公司 | Alkaline zinc-manganese battery diaphragm and preparation process thereof |
| CN112126113A (en) * | 2020-09-24 | 2020-12-25 | 湖南省凯纳方科技有限公司 | Surface grafting modifier for mh-ni battery diaphragm |
| CN112928387A (en) * | 2021-01-28 | 2021-06-08 | 厦门大学 | Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4192908A (en) * | 1979-06-15 | 1980-03-11 | The United States Of America As Represented By The Secretary Of The Navy | Mass-transport separator for alkaline nickel-zinc cells and cell |
| US4279978A (en) * | 1980-05-23 | 1981-07-21 | Energy Research Corporation | Battery separator employing zinc selective additive materials |
| US5591539A (en) * | 1993-04-13 | 1997-01-07 | Pall Corporation | Electrolytically conductive battery separator polymeric film |
| US5318866A (en) * | 1993-04-23 | 1994-06-07 | Pall Corporation | Battery separators |
| US5492781A (en) * | 1994-01-18 | 1996-02-20 | Pall Corporation | Battery separators |
-
2004
- 2004-06-16 CN CNB2004100251769A patent/CN100452485C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728505B (en) * | 2009-12-18 | 2013-04-03 | 河南科高辐射化工科技有限公司 | Alkaline zinc-manganese battery diaphragm and preparation process thereof |
| CN112126113A (en) * | 2020-09-24 | 2020-12-25 | 湖南省凯纳方科技有限公司 | Surface grafting modifier for mh-ni battery diaphragm |
| CN112928387A (en) * | 2021-01-28 | 2021-06-08 | 厦门大学 | Boron-containing modified diaphragm, preparation method and application thereof, and battery containing diaphragm |
| WO2022161438A1 (en) * | 2021-01-28 | 2022-08-04 | 厦门大学 | Boron-containing modified diaphragm and preparation method and application therefor, and battery including diaphragm |
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| Publication number | Publication date |
|---|---|
| CN100452485C (en) | 2009-01-14 |
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Granted publication date: 20090114 Termination date: 20120616 |