CN102683732A - Proton exchange membrane made from high polymer-metal complex-heteropoly acid material and preparation method thereof - Google Patents

Proton exchange membrane made from high polymer-metal complex-heteropoly acid material and preparation method thereof Download PDF

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CN102683732A
CN102683732A CN2012101541299A CN201210154129A CN102683732A CN 102683732 A CN102683732 A CN 102683732A CN 2012101541299 A CN2012101541299 A CN 2012101541299A CN 201210154129 A CN201210154129 A CN 201210154129A CN 102683732 A CN102683732 A CN 102683732A
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high polymer
metal complex
side chain
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CN102683732B (en
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吴锦明
沈爱宝
王南平
史春越
陈婷婷
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Nantong University
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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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/30—Hydrogen technology
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Abstract

The invention discloses a proton exchange membrane made from a high polymer-metal complex-heteropoly acid material and a preparation method thereof. The preparation method comprises the following steps of: introducing a side chain onto a high polymer; introducing an organic ligand onto the side chain; preparing an organic ligand; introducing a multi-tooth ligand onto the side chain; generating a high molecular metal complex; introducing heteropoly acid at the tail end of the side chain; preparing a film with a tape casting method; and the like. As proved by testing, the proton conductivity of the proton exchange membrane prepared by the method is up to the magnitude order level of 10-2S/cm at the temperature of 100-140 DEG C, the methanol crossover coefficient is lower than the magnitude order of 10<-8>-10<-7> cm<2>/s, and the use requirement of a fuel cell, in particular a methanol fuel battery proton exchange membrane can be met.

Description

The PEM of high polymer-metal complex-heteropolyacid material and preparation method
Technical field
The present invention relates to the fuel cell technology field, particularly relate to a kind of PEM that methyl alcohol or alcohol fuel cell use and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is efficient, the green energy resource device that a kind of chemical energy with fuel such as hydrogen or methyl alcohol is converted into electric energy, has extremely wide application prospect.Methanol fuel cell has potential actual application prospect owing to have advantages such as charging is convenient, the battery pile system configuration is simple, the response time is short aspect compact power.PEM is the core component of fuel cell, plays at inside battery and isolates fuel and oxidant, and the effect that proton channel is provided.With the Nafion series membranes of du pont company production is that the perfluorinated sulfonic acid PEM of representative has advantages such as proton conductivity is high under the low temperature and high humidity, mechanical strength is big; But exist also simultaneously that price height, methanol permeability are big, the low defective of proton conductivity under the dehydration condition, limited the large-scale commercial applications application of Proton Exchange Membrane Fuel Cells.
Poly aromatic compound (like PAEK, polyarylether, polyimides, polyphosphazene etc.) has good thermal stability and mechanical performance; After introducing sulfonic group; Not only can inherit original superior function, but also have proton-conducting, therefore become the research focus of floride-free PEM.Compare with perfluoro sulfonic acid membrane, the sulfonated poly aromatic compound has advantage at aspects such as heat-resisting quantity, alcohol-rejecting ability, price, processing characteristicies, but that defective is a proton conductivity is on the low side.Increase the sulfonation degree of poly aromatic compound,, even can reach the level close with perfluoro sulfonic acid membrane though can improve proton conductivity, this moment film alcohol-rejecting ability and mechanical performance variation, can not satisfy the condition of work of battery.
The preparation composite membrane is a kind of common method that existing PEM is carried out modification, at high temperature still can keep the high and big characteristics of mechanical strength of proton conductivity like polybenzimidazoles (PBI) film that adsorbs inorganic acid; Utilize heteropoly acid to be rich in the characteristic of the crystallization water and high proton electrical conductance, the composite membrane of doping heteropoly acid can surpass 100 ℃ with the anhydrous condition high proton conductivity of maintenance down; But inorganic acid or heteropoly acid are prone to be dissolved in water, and under the operation of fuel cells condition, the water that very easily generates with fuel cell reaction oozes out from film, causes the proton conductivity of film sharply to descend.Blended metal oxide in composite membrane (like silicon dioxide, titanium dioxide and zirconium dioxide etc.) is though can improve the resistance to elevated temperatures and the alcohol-rejecting ability of film; Also can slow down the stripping of heteropoly acid to a certain extent; But itself does not have proton-conducting these metal oxides, and the excessive affiliation that adds causes proton conductivity sharply to descend.Over all, the composite membrane performance for preparing at present is imperfection also, needs between the multiple performance of film, carry out balance and selects; The proton exchange composite membrane of function admirable, suitable operation of fuel cells awaits further to study.
Summary of the invention
The object of the present invention is to provide that a kind of high electricity is led, the PEM and the preparation method of resistant to elevated temperatures high polymer-metal complex-heteropolyacid material.
Technical solution of the present invention is:
The PEM of a kind of high polymer-metal complex-heteropolyacid material is characterized in that: said high polymer-metal complex-heteropolyacid material is formula (VII) compound:
Figure BDA00001645117800031
Wherein X=O, SO 2Or CO; M=Ni, Cu, Co, Zn, Mn, Fe or Pd;
HPA=H 3PW 12O 40, H 3PMo 12O 40, H 4PMo 11VO 40, H 5PMo 10V 2O 40Or H 6PMo 9V 3O 40
The chemical nature of high polymer main chain is poly aromatic ether, polysulfones ether or polyethers ketone.
The preparation method of the PEM of a kind of high polymer-metal complex-heteropolyacid material is characterized in that: comprise the following steps:
(1) introduces side chain on the high polymer: formula (I) high polymer and formaldehyde and hydrochloric acid reaction are obtained formula (II) compound;
(2) introducing of organic ligand on the side chain: with formula (II) compound and 2,5-4-dihydroxy benzaldehyde and potash hybrid reaction obtain formula (III) compound;
(3) preparation of organic ligand:, obtain formula (IV) compound, as the organic ligand of side chain metal complex with salicylide and diamine compounds reaction;
(4) introducing of multidentate ligand on the side chain: with formula (III) compound and formula (IV) compound 1～3h that dewaters that in organic solvent, refluxes, concentrate, suction filtration obtains formula (V) compound;
(5) generation of high molecular metal complex: formula (V) compound and metal chloride reaction obtain formula (VI) compound;
(6) introducing of side chain terminal heteropoly acid: formula (VI) compound and heteropoly acid reaction obtain formula (VII) compound;
(7) curtain coating legal system film: formula (VII) compound is dissolved in DMF or DMAc, and curtain coating legal system film obtains being used for the PEM of fuel cell;
The reaction equation of above-mentioned steps (1)～(6) is:
Figure BDA00001645117800041
Figure BDA00001645117800051
High polymer described in the above-mentioned steps (1) is meant poly aromatic ether or polysulfones ether or polyether-ketone family macromolecule.
Diamine compounds is meant o-phenylenediamine or ethylenediamine described in the above-mentioned steps (3).
Organic solvent described in the above-mentioned steps (4) can be benzene, toluene, cyclohexane.
Metal chloride can be the chloride of nickel ion, copper ion, cobalt ions, zinc ion, manganese ion, iron ion, palladium ion described in the above-mentioned steps (5).
Heteropoly acid described in the above-mentioned steps (6) is meant the substituted phosphomolybdic acid of phosphotungstic acid or phosphomolybdic acid or vanadium.
The PEM of the present invention's preparation reaches 10 through the proton conductivity of testing at 100～140 ℃ -2S/cm order of magnitude level, the methanol crossover coefficient is less than 10 -8～10 -7Cm 2The order of magnitude of/s can satisfy the particularly instructions for use of methanol fuel cell PEM of fuel cell.
The present invention compares with existing PEM and technology of preparing, has following characteristics and corresponding advantages:
Replace sulfonic group that the proton conduction passage is provided with heteropoly acid; Make the proton conduction process can not rely on the secondary water source; Because heteropoly acid itself carries a large amount of crystallizations water; Even still having a certain amount of crystallization water more than 100 ℃ and combining water, the PEM that therefore the present invention relates to has the high temperature proton-conducting;
Selecting poly aromatic ether or polysulfones ether or polyethers ketone is main chain, advantage such as make that the PEM that the present invention relates to can keep that the original methanol permeability of these high polymers is little, Heat stability is good, mechanical strength are big;
The existing main chain of proton exchange membrane material molecule that the present invention relates to has side chain again, and heteropoly acid is positioned at side chain terminal, makes it have enough pliabilities, is convenient to film and forms unobstructed proton channel, and this structurally lays the foundation for it has high proton conductivity;
Utilize electrostatic attraction, heteropoly acid is anchored on the metal-polymer, heteropoly acid is combined firmly with macromolecule, thereby guaranteed that the PEM that the present invention relates to has good durability in real work.
Below in conjunction with embodiment the present invention is described further.
Embodiment
Embodiment 1
(1) 5g polyphenylene oxide is dissolved among 100 milliliters of DMF, adds 1g polyformaldehyde and 5mL concentrated hydrochloric acid,, pour in the frozen water, filter in 30 ℃ of reaction 5h, washing, 60 ℃ of following vacuumizes obtain product A (polyphenylene oxide of chloromethylation).
(2) with product A, the 2g 2 of above-mentioned preparation; The 5-4-dihydroxy benzaldehyde is dissolved among the DMF, adds the 2g Anhydrous potassium carbonate, 100 ℃ of stirring reaction 4h; Decompression concentrates drains solvent; Add water and stir, inorganic salts are removed in washing, and vacuumize obtains product B (side chain connects the polyphenylene ether compound of phenolic aldehyde ether).
(3) 1.22g salicylide and 1.08g o-phenylenediamine are dissolved in the absolute ethyl alcohol, stirring reaction 4h filters and to obtain product C (salicylide list contract o-phenylenediamine solid).
(4) product B and product C are dissolved in toluene, backflow dewaters, and concentrates, and suction filtration obtains product D (side chain contains the polyphenylene ether compound of phenolic hydroxyl group, western Buddhist alkali multidentate ligand).
(5) product D is dissolved in ethanol, adds the manganese chloride ethanolic solution, stirring reaction 1h concentrates, and suction filtration obtains product E (side chain contains the polyphenylene ether compound of manganese complex).
(6) above-mentioned synthetic product E is dissolved in organic solvent, adds the dissolve with ethanol of phosphotungstic acid, stirring reaction 2h concentrates, and suction filtration obtains formula (VII) compound (polyphenylene oxide-manganese complex-phosphotungstic acid macromolecular compound).
(7) synthetic phosphotungstic acid-manganese metal macromolecular compound is dissolved in the organic solvent such as DMF, The tape casting is processed PEM.
Embodiment 2
Operating procedure is similar with example 1, only in the step (6) phosphotungstic acid is replaced with phosphomolybdic acid, obtains containing the PEM of polyphenylene oxide-manganese complex-phosphomolybdic acid macromolecular compound.
Embodiment 3
Operating procedure is similar with example 1, only in step (5), replaces the PEM that manganese chloride obtains containing polyphenylene oxide-Zn complex-phosphotungstic acid macromolecular compound with zinc chloride.
The physicochemical property of above-mentioned 3 routine gained high polymer-metal complexs-heteropoly acid ternary coupling proton exchange membrane material or film is listed in the table below:
Figure BDA00001645117800071
Figure BDA00001645117800081
The foregoing description is the preferable implementation method of the present invention; But implementation method of the present invention is not restricted to the described embodiments; Other is any not to deviate from change, the modification done under spirit of the present invention and the principle, substitute, combination, simplify the substitute mode that is equivalence, is included within protection scope of the present invention.

Claims (3)

1. the PEM of high polymer-metal complex-heteropolyacid material, it is characterized in that: said high polymer-metal complex-heteropolyacid material is formula (VII) compound:
Figure FDA00001645117700011
Wherein X=O, SO 2Or CO; M=Ni, Cu, Co, Zn, Mn, Fe or Pd;
HPA=H 3PW 12O 40, H 3PMo 12O 40, H 4PMo 11VO 40, H 5PMo 10V 2O 40Or H 6PMo 9V 3O 40
2. the PEM of high polymer-metal complex according to claim 1-heteropolyacid material is characterized in that: the chemical nature of high polymer main chain is poly aromatic ether, polysulfones ether or polyethers ketone.
3. the preparation method of the PEM of high polymer-metal complex-heteropolyacid material is characterized in that: comprise the following steps:
(1) introduces side chain on the high polymer: formula (I) high polymer and formaldehyde and hydrochloric acid reaction are obtained formula (II) compound;
(2) introducing of organic ligand on the side chain: with formula (II) compound and 2,5-4-dihydroxy benzaldehyde and potash hybrid reaction obtain formula (III) compound;
(3) preparation of organic ligand:, obtain formula (IV) compound, as the organic ligand of side chain metal complex with salicylide and diamine compounds reaction;
(4) introducing of multidentate ligand on the side chain:, obtain formula (V) compound with formula (III) compound and the reaction of formula (IV) compound;
(5) generation of high molecular metal complex: formula (V) compound and metal chloride reaction obtain formula (VI) compound;
(6) introducing of side chain terminal heteropoly acid: formula (VI) compound and heteropoly acid reaction obtain formula (VII) compound;
(7) curtain coating legal system film: formula (VII) compound is dissolved in DMF or DMAc, and curtain coating legal system film obtains being used for the PEM of fuel cell;
The reaction equation of above-mentioned steps (1)～(6) is:
Figure FDA00001645117700031
CN201210154129.9A 2012-05-16 2012-05-16 Proton exchange membrane made from high polymer-metal complex-heteropoly acid material and preparation method thereof Expired - Fee Related CN102683732B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784946A (en) * 2016-12-01 2017-05-31 长春工业大学 Fuel cell polyfluorene ether nitrile cross-linking type anion exchange membrane material of cation group functionalization and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006080766A1 (en) * 2005-01-25 2006-08-03 Industry-University Cooperation Foundation, Hanyang University Acid or base-doped proton conducting polymer, preparation method thereof, polymer membrane using the same and fuel cell using the same
CN101867050A (en) * 2010-06-08 2010-10-20 南通大学 Composite proton exchange membrane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006080766A1 (en) * 2005-01-25 2006-08-03 Industry-University Cooperation Foundation, Hanyang University Acid or base-doped proton conducting polymer, preparation method thereof, polymer membrane using the same and fuel cell using the same
CN101867050A (en) * 2010-06-08 2010-10-20 南通大学 Composite proton exchange membrane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HAIBO ZHANG等: "Sulfonated poly(arylene ether nitrile ketone) and its composite with phosphotungstic acid as materials for proton exchange membranes", 《SULFONATED POLY(ARYLENE ETHER NITRILE KETONE) AND ITS COMPOSITE WITH PHOSPHOTUNGSTIC ACID AS MATERIALS FOR PROTON EXCHANGE MEMBRANES》 *
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784946A (en) * 2016-12-01 2017-05-31 长春工业大学 Fuel cell polyfluorene ether nitrile cross-linking type anion exchange membrane material of cation group functionalization and preparation method thereof
CN106784946B (en) * 2016-12-01 2019-04-02 长春工业大学 Polyfluorene ether nitrile cross-linking type anion exchange membrane material of fuel cell cation group functionalization and preparation method thereof

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