CN104716352A - Use of crosslinking type polybenzimidazole porous separating membrane in liquid flow battery - Google Patents

Use of crosslinking type polybenzimidazole porous separating membrane in liquid flow battery Download PDF

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Publication number
CN104716352A
CN104716352A CN201310693023.0A CN201310693023A CN104716352A CN 104716352 A CN104716352 A CN 104716352A CN 201310693023 A CN201310693023 A CN 201310693023A CN 104716352 A CN104716352 A CN 104716352A
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polybenzimidazoles
flow battery
copolymer
diffusion barrier
membrane
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CN201310693023.0A
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Inventor
李先锋
张华民
段寅琦
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to use of a crosslinking type polybenzimidazole porous separating membrane in a liquid flow battery, and the porous membrane material is a crosslinking type polybenzimidazole polymer material. The porous membrane prepared by the invention is used in the liquid flow battery, by use of a cross-linking method and controlling of the crosslinking reaction, the membrane material oxidation stability and ion selectivity can be improved, the function of an ion exchange membrane in the liquid flow battery can be realized, the problem of capacity attenuation of a porous diaphragm can be effectively solved, the aperture of the porous membrane can be further regulated by change of variety of the polymer and the crosslinking agent of the composite membrane, ion selectivity of the porous membrane can be effectively improved, and the membrane material has the advantages of simple preparation method, controllable pore size, low cost, and easy implementation of large batch production.

Description

The application of cross-linking type polybenzimidazoles porous diffusion barrier in flow battery
Technical field
The present invention relates to porous diffusion barrier, the particularly application of this porous diffusion barrier in flow battery.
Background technology
Flow battery is a kind of electrochemical energy storage new technology, compared with other energy storage technology, have that energy conversion efficiency is high, system is flexible, capacitance of storage is large, addressing is free, can the advantage such as deep discharge, safety and environmental protection, maintenance cost be low, the aspects such as the energy storage of the renewable energy power generation such as wind energy, solar energy, emergency power system, stand-by station and electric power system peak load shifting can be widely used in.All-vanadium flow battery (Vanadium flow battery, VFB), because fail safe is high, good stability, efficiency are high, the life-span is long (life-span >15), low cost and other advantages, is considered to have good application prospect.
Battery diaphragm is the important component part in flow battery, and it plays and intercepts positive and negative electrode electrolyte solution, and proton conducting forms circuit in battery.Proton-conducting, the ion selectivity and oxidation stability etc. of film directly will affect chemical property and the useful life of battery; Therefore require that film has lower vanadium ion permeability (namely having higher selectivity) and lower surface resistance (namely having higher ionic conductance), also should have good chemical stability and lower cost simultaneously.The Nafion film of the membrane material both at home and abroad used now mainly du pont company's exploitation, Nafion film has excellent performance in chemical property and useful life etc., but due to expensive, the shortcomings such as ion selectivity difference, limit the application in flow battery of this film.Therefore, the battery diaphragm with high selectivity, high stability and low cost is developed most important.
In VRB, vanadium ion and proton all exist with the form of hydrated ion.Due to the difference of vanadium ion and hydrogen ion hydration radius and charge density, can by having pore separation membrane to realize to vanadium ion and hydrionic Selective Separation.Using perforated film as VRB barrier film, have that chemical stability is good, material selection wide ranges, technical maturity easily amplify, the advantages such as production cost is low.Perforated film to the obstruct of vanadium ion and to hydrionic selectivity through being realized by the aperture control of film.Therefore, on the basis optimizing aperture, improve its selective penetrated property further, and then improve its VRB performance, there is important Practical significance.
Polybenzimidazoles take benzimidazole as the polymer of predominant repeat unit, owing to there is the fragrant heterocycle of conjugation in strand, maintains the hexahedral arrangement architecture of polymer fragrance, thus have excellent thermal stability, chemical stability and mechanical property.Polybenzimidazoles has good application prospect at separation field due to its excellent thermal stability and mechanical stability.In petrochemical industry, utilize the feature such as heat-resisting fire-resistant, chemical-resistant reagent of PBI fiber, the filter cloth made or fabric can be used for that industrial products filter, waste water and mud class are filtered, silt trapping, flue gas and air filtration, high temperature or corrosive materials transmission etc.The reverse osmosis membrane that PBI makes and doughnut also can be used for seawater desalination and gas separaion.The heat that the present invention utilizes PBI good, mechanical stability and chemical stability, by the ion selectivity of crosslinked raising PBI film in flow battery environment and oxidation stability, the excellent porous diffusion barrier of processability.
Summary of the invention
The object of the present invention is to provide a kind of cross-linking type polybenzimidazoles solvent resistant NF membrane material being applicable to all-vanadium flow battery.This material has excellent heat stability, mechanical stability and chemical stability.The present invention, adopts crosslinked method, controls cross linking conditions, can improve membrane material oxidation stability performance and ion selectivity.For realizing this object, the technical solution used in the present invention is:
Described porous diffusion barrier material is cross-linking type polybenzimidazoles macromolecular material,
Described polybenzimidazoles is homopolymers, and homopolymers general structure is as follows:
Wherein R 1one in following structure:
Wherein n representation polymer construction unit number is the positive integer of 10-200; R 2and R 3be respectively hydrogen atom, C 1-C 4saturated alkane group or C 2-C 4one in unsaturated alkane group, R 2and R 3it can be identical or different group;
Or described polybenzimidazoles is copolymer, and copolymer structure general formula is as follows,
Copolymer can be random copolymer or block copolymer, wherein m, n representation polymer construction unit number, is the positive integer of 10-200,0 < n/m+n≤0.8,0.2≤m/m+n < 1;
Wherein R 1one of following structure is represented respectively with R2:
R 3and R 4be respectively hydrogen atom, C 1-C 4saturated alkane group or C 2-C 4one in unsaturated alkane group, R 3and R 4it can be identical or different group.
Described polybenzimidazoles is copolymer, works as R 1for following construction unit a period of time containing pyridine groups,
R 2can one of structure of ehter bond and different substituents be contained:
Wherein: R 3and R 4be respectively hydrogen atom, C 1-C 4saturated alkane group or C 2-C 4one in unsaturated alkane group, R 3and R 4it can be identical or different group.
In addition, the copolymer of above-mentioned polybenzimidazoles can be random copolymer also can be block copolymer.
Wherein the preparation process of polyalcohol stephanoporate diffusion barrier is as follows:
Be dissolved in by described polybenzimidazoles in one or two or more kinds solvent of DMSO, DMF and DMAC or be dissolved in the mixed solvent of DMSO, DMF and DMAC one or two or more kinds and THF and/or n-hexane, forming concentration is the polymer solution of 5-40wt%;
Be applied to by polymer solution on glass plate or nonwoven fabrics, volatilize the solution coated 0-20 minute in atmosphere, is then immersed in the water 1-60 minute, and form polybenzimidazoles porous diffusion barrier, film thickness is at 20-1000um
Polybenzimidazoles porous diffusion barrier is soaked in the solution containing crosslinking agent, under 25-100 DEG C of condition, soaks 0.5-200 hour, obtain cross-linking type polybenzimidazoles porous diffusion barrier.
Described crosslinking agent is dihalogenated alkane or aromatic hydrocarbon, as adjacent dichloro benzyl benzene, a dichloro benzyl benzene, to dichloro benzyl benzene, dichloroethanes, dichloropropane, dichloroetane, as adjacent dibromo-benzyl benzene, a dibromo-benzyl benzene, to one or two or more kinds in dibromo-benzyl benzene, Bromofume, dibromopropane, dibromobutane; Solution solvent is the mixed solvent of one or two or more kinds in methyl alcohol, ethanol, isopropyl alcohol, butanols.
The concentration of described crosslinking agent at 1-60wt%, reaction temperature 25-60 degree, crosslinking time 2-20 hour.
In solvent or mixed solvent, one or two or more kinds volume content of DMSO, DMF and DMAC is 70-100wt%.
Described liquid flow energy storage battery comprises all-vanadium liquid flow energy storage battery, zinc/bromine flow battery, sodium polysulfide/bromine redox flow cell, iron/chrome liquor galvanic battery, vanadium/bromine flow battery or zinc/cerium flow battery.
The weight average molecular weight of copolymer is between 5000-800000.
Beneficial effect
1. the perforated membrane that prepared by the present invention is applied in flow battery, adopt crosslinked method, by controlling the reaction be cross-linked, improve membrane material oxidation stability performance and ion selectivity, the function of amberplex in flow battery can be realized, efficiently solve the capacity fade problem of porous septum simultaneously;
2. the composite membrane that prepared by the present invention regulates and controls the aperture of perforated membrane further by the kind changing polymer and crosslinking agent, effectively improve ion selectivity and the ion selectivity of perforated membrane;
3. such membrane material preparation method is simple, and aperture is controlled, with low cost, easily realizes producing in enormous quantities;
4. the present invention has widened kind and the scope of application of flow battery membrane material;
5. the present invention can realize the controllability to flow battery efficiency.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of polybenzimidazole resin;
One of sectional view of Fig. 2 porous diffusion barrier prepared by embodiment 1;
The sectional view two of Fig. 3 porous diffusion barrier prepared by embodiment 1.
Embodiment
Embodiment 1
The polybenzimidazoles (weight average molecular weight is about 50000) 10g with following structure is dissolved in the DMA of 50ml, makes the polymer solution of 20%.By solution-cast on glass plate, be bulldozed with casting film cutter.Then immerse in 5L water rapidly, solidify 5 minutes, be formed with pore separation membrane (Fig. 1), obtain the perforated membrane of polybenzimidazoles.The porous diffusion barrier of polybenzimidazoles is cross-linked 24 hours in the methanol solution of 5% pair of dichloro benzyl benzene, obtains cross-linking type polyphenyl imipramine film.
The construction unit number of n representation polymer, 10≤n≤200.
Wherein Fig. 2 gives the cross section electron microscopic picture of solvent resistant NF membrane prepared by embodiment 1, membrane material shows conventional finger-type pore structure, utilize the cross-linking type polybenzimidazoles porous diffusion barrier assembling all-vanadium flow battery of preparation, wherein Catalytic Layer is activated carbon-fiber felt, bipolar plates is graphite cake, and the effective area of film is 6cm -2, both positive and negative polarity electrolyte volume is 30ml, and wherein vanadium ion concentration is 1.50mol L -1, H 2sO 4concentration is 3mol L -1.In charge-discharge test, battery charging and discharging current density is 80mA cm -2, battery coulombic efficiency is 98.8%, and energy efficiency is 86%.
Comparative example 1
Preparation method with embodiment 1, but does not carry out cross-linking reaction, i.e. pure polybenzimidazoles perforated membrane, battery coulombic efficiency: 94%, energy efficiency: 82%.Can find out that cross-linking reaction can improve the ion selection type of battery effectively, coulombic efficiency increases substantially.
Embodiment 2
3.4 grams of phosphorus pentoxides are dissolved in 34 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heat up after stirring formation settled solution, then 6mmol biphenyl tetramine is added, 6mmol4,4 '-dicarboxydiphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution containing 5%., fully wash with water after 24 hours in placement, until solution is in neutral.Filter, dry.The polymer of preparation is dissolved in DMAC the solution preparing 15wt%, by solution-cast on glass plate, is bulldozed with casting film cutter.Then immerse in 5L water rapidly, solidify 5 minutes, be formed with pore separation membrane, obtain the perforated membrane of polybenzimidazoles.The porous diffusion barrier of polybenzimidazoles is cross-linked 24 hours in the methanol solution of 5% pair of dichloro benzyl benzene, obtains that there is following chemical constitution porous diffusion barrier.
The construction unit number of n representation polymer in embodiment, 10≤n≤200.
The infrared spectrum of polymer is shown in Fig. 2, confirms the structure of prepared polymer.
Embodiment 3
With embodiment 1, change polybenzimidazoles structure into following structure, weight average molecular weight is about 50000.
The construction unit number of n representation polymer in embodiment, 10≤n≤200.
Embodiment 4
With embodiment 3, change polybenzimidazoles structure into following structure, weight average molecular weight is about 70000.
The construction unit number of n representation polymer in embodiment, 10≤n≤200.
Embodiment 5
With embodiment 4, change polybenzimidazoles structure into following structure, polymer average molecular weight is about 40000.
The construction unit number of n representation polymer in embodiment, 10≤n≤200.
Embodiment 6
With embodiment 5, polybenzimidazoles copolymer is changed into the copolymer of the polybenzimidazoles of following structure, polymer average molecular weight is about 50000.
The construction unit number of n and m representation polymer in embodiment, 10≤n≤200,10≤m≤200.In charge-discharge test, battery charging and discharging current density is 80mA cm -2, battery coulombic efficiency is 97.6%, and energy efficiency is 85%.
Comparative example 2
Preparation method with embodiment 6, but does not carry out cross-linking reaction, i.e. pure polybenzimidazoles perforated membrane, battery coulombic efficiency: 93.5%, energy efficiency: 81%.Can find out that cross-linking reaction can improve the ion selectivity of battery effectively, coulombic efficiency increases substantially.

Claims (8)

1. the application of cross-linking type polybenzimidazoles porous diffusion barrier in flow battery, is characterized in that: described porous diffusion barrier material is cross-linking type polybenzimidazoles macromolecular material,
Described polybenzimidazoles is homopolymers, and homopolymers general structure is as follows:
Wherein R 1one in following structure:
Wherein n representation polymer construction unit number is the positive integer of 10-200; R 2and R 3be respectively hydrogen atom, C 1-C 4saturated alkane group or C 2-C 4one in unsaturated alkane group, R 2and R 3it can be identical or different group;
Or described polybenzimidazoles is copolymer, and copolymer structure general formula is as follows,
Copolymer can be random copolymer or block copolymer, wherein m, n representation polymer construction unit number, is the positive integer of 10-200,0 < n/m+n≤0.8,0.2≤m/m+n < 1;
Wherein R 1one of following structure is represented respectively with R2:
R 3and R 4be respectively hydrogen atom, C 1-C 4saturated alkane group or C 2-C 4one in unsaturated alkane group, R 3and R 4it can be identical or different group.
2. application according to claim 1, is characterized in that, described polybenzimidazoles is copolymer, works as R 1for following construction unit a period of time containing pyridine groups,
R 2can one of structure of ehter bond and different substituents be contained:
Wherein: R 3and R 4be respectively hydrogen atom, C 1-C 4saturated alkane group or C 2-C 4one in unsaturated alkane group, R 3and R 4it can be identical or different group.
3. application according to claim 1, is characterized in that, described cross-linking type polybenzimidazoles porous diffusion barrier preparation process is as follows:
1) be dissolved in by polybenzimidazoles according to claim 1 in one or two or more kinds solvent of DMSO, DMF and DMAC or be dissolved in the mixed solvent of DMSO, DMF and DMAC one or two or more kinds and THF and/or n-hexane, forming concentration is the polymer solution of 5-40wt%;
2) be applied to by polymer solution on glass plate or nonwoven fabrics, volatilize the solution coated 0-20 minute in atmosphere, is then immersed in the water 1-60 minute, and form polybenzimidazoles porous diffusion barrier, film thickness is at 20-1000um;
3) polybenzimidazoles porous diffusion barrier is soaked in the solution containing crosslinking agent, under 25-100 DEG C of condition, soaks 0.5-200 hour, obtain cross-linking type polybenzimidazoles porous diffusion barrier.
4. application according to claim 3, it is characterized in that, described crosslinking agent is dihalogenated alkane or aromatic hydrocarbon, as adjacent dichloro benzyl benzene, a dichloro benzyl benzene, to dichloro benzyl benzene, dichloroethanes, dichloropropane, dichloroetane, as adjacent dibromo-benzyl benzene, a dibromo-benzyl benzene, to one or two or more kinds in dibromo-benzyl benzene, Bromofume, dibromopropane, dibromobutane; Solution solvent is the mixed solvent of one or two or more kinds in methyl alcohol, ethanol, isopropyl alcohol, butanols.
5. application according to claim 3, is characterized in that, the concentration of described crosslinking agent at 1-60wt%, reaction temperature 25-60 degree, crosslinking time 2-20 hour.
6. application according to claim 1, is characterized in that:
In solvent or mixed solvent, one or two or more kinds volume content of DMSO, DMF and DMAC is 70-100wt%.
7. application according to claim 1, is characterized in that: described flow battery comprises all-vanadium flow battery, zinc/bromine flow battery, sodium polysulfide/bromine redox flow cell, iron/chrome liquor galvanic battery, vanadium/bromine flow battery or zinc/cerium flow battery.
8. application according to claim 1, is characterized in that: the weight average molecular weight of copolymer is between 5000-800000.
CN201310693023.0A 2013-12-15 2013-12-15 Use of crosslinking type polybenzimidazole porous separating membrane in liquid flow battery Pending CN104716352A (en)

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CN106558711A (en) * 2015-09-21 2017-04-05 中国科学院大连化学物理研究所 A kind of application of porous septum in organic system flow battery
CN106558712A (en) * 2015-09-21 2017-04-05 中国科学院大连化学物理研究所 A kind of application of composite membrane in neutral system zinc-iron flow battery
CN106876630A (en) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 A kind of application of crosslinked polyethers acid imide porous septum in lithium ion battery
WO2018103517A1 (en) * 2016-12-10 2018-06-14 中国科学院大连化学物理研究所 Alkaline zinc-iron flow battery
CN108400362A (en) * 2018-02-05 2018-08-14 大连理工大学 A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof
CN108649255A (en) * 2018-05-12 2018-10-12 中国科学院山西煤炭化学研究所 Polybenzimidazoles proton exchange membrane and preparation method and application
CN108878936A (en) * 2018-07-03 2018-11-23 大连理工大学 A kind of hydrophobic side chain modification alkyl sulfonate polybenzimidazole amphoteric membrane and preparation method thereof
CN108912362A (en) * 2018-07-17 2018-11-30 大连理工大学 A kind of polyamine functional polybenzimidazoles cross linking membrane and preparation method
CN109863227A (en) * 2016-08-04 2019-06-07 西蒙弗雷泽大学 The crosslinking of hydroxide stable polybenzimidazoles and polyimidazole film and ionomer
CN110993998A (en) * 2019-12-03 2020-04-10 中国科学院山西煤炭化学研究所 Polybenzimidazole proton exchange membrane containing naphthalene ring and preparation method and application thereof
US20200266406A1 (en) * 2017-10-09 2020-08-20 Shanghai Energy New Materials Technology Co., Ltd. Separators, electrochemical devices comprising the separator, and methods for making the separator
CN112126105A (en) * 2020-09-18 2020-12-25 上海交通大学 Polybenzimidazole/phosphoric acid composite membrane prepared by online crosslinking method and preparation method thereof
CN112251774A (en) * 2020-09-01 2021-01-22 中国科学院山西煤炭化学研究所 Polybenzimidazole-based porous polymer ion exchange membrane and preparation method and application thereof by adopting sol-gel method
CN112940321A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Cross-linked composite membrane for flow battery and preparation and application thereof

Cited By (19)

* Cited by examiner, † Cited by third party
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CN106558712A (en) * 2015-09-21 2017-04-05 中国科学院大连化学物理研究所 A kind of application of composite membrane in neutral system zinc-iron flow battery
CN106558711A (en) * 2015-09-21 2017-04-05 中国科学院大连化学物理研究所 A kind of application of porous septum in organic system flow battery
CN106558711B (en) * 2015-09-21 2019-06-11 中国科学院大连化学物理研究所 A kind of application of porous septum in organic system flow battery
CN106876630A (en) * 2015-12-13 2017-06-20 中国科学院大连化学物理研究所 A kind of application of crosslinked polyethers acid imide porous septum in lithium ion battery
CN109863227A (en) * 2016-08-04 2019-06-07 西蒙弗雷泽大学 The crosslinking of hydroxide stable polybenzimidazoles and polyimidazole film and ionomer
CN109863227B (en) * 2016-08-04 2023-01-10 西蒙弗雷泽大学 Hydroxide-stabilized polybenzimidazolium and polyimidazolium membranes and ionomers crosslinking
WO2018103517A1 (en) * 2016-12-10 2018-06-14 中国科学院大连化学物理研究所 Alkaline zinc-iron flow battery
US20200266406A1 (en) * 2017-10-09 2020-08-20 Shanghai Energy New Materials Technology Co., Ltd. Separators, electrochemical devices comprising the separator, and methods for making the separator
CN108400362A (en) * 2018-02-05 2018-08-14 大连理工大学 A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof
CN108649255A (en) * 2018-05-12 2018-10-12 中国科学院山西煤炭化学研究所 Polybenzimidazoles proton exchange membrane and preparation method and application
CN108878936A (en) * 2018-07-03 2018-11-23 大连理工大学 A kind of hydrophobic side chain modification alkyl sulfonate polybenzimidazole amphoteric membrane and preparation method thereof
CN108912362A (en) * 2018-07-17 2018-11-30 大连理工大学 A kind of polyamine functional polybenzimidazoles cross linking membrane and preparation method
CN108912362B (en) * 2018-07-17 2021-01-19 大连理工大学 Polyamine functionalized polybenzimidazole crosslinked membrane and preparation method thereof
CN110993998A (en) * 2019-12-03 2020-04-10 中国科学院山西煤炭化学研究所 Polybenzimidazole proton exchange membrane containing naphthalene ring and preparation method and application thereof
CN112940321A (en) * 2019-12-10 2021-06-11 中国科学院大连化学物理研究所 Cross-linked composite membrane for flow battery and preparation and application thereof
CN112940321B (en) * 2019-12-10 2022-04-15 中国科学院大连化学物理研究所 Cross-linked composite membrane for flow battery and preparation and application thereof
CN112251774A (en) * 2020-09-01 2021-01-22 中国科学院山西煤炭化学研究所 Polybenzimidazole-based porous polymer ion exchange membrane and preparation method and application thereof by adopting sol-gel method
CN112251774B (en) * 2020-09-01 2022-03-11 中国科学院山西煤炭化学研究所 Polybenzimidazole-based porous polymer ion exchange membrane and preparation method and application thereof by adopting sol-gel method
CN112126105A (en) * 2020-09-18 2020-12-25 上海交通大学 Polybenzimidazole/phosphoric acid composite membrane prepared by online crosslinking method and preparation method thereof

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Application publication date: 20150617