CN102002167A - Proton exchange membrane applied to direct methanol fuel cell and preparation method thereof - Google Patents

Proton exchange membrane applied to direct methanol fuel cell and preparation method thereof Download PDF

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CN102002167A
CN102002167A CN2010105267754A CN201010526775A CN102002167A CN 102002167 A CN102002167 A CN 102002167A CN 2010105267754 A CN2010105267754 A CN 2010105267754A CN 201010526775 A CN201010526775 A CN 201010526775A CN 102002167 A CN102002167 A CN 102002167A
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proton exchange
porphyrin
nafion
film
porphyrin compound
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于非
张果戈
周震涛
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South China University of Technology SCUT
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South China University of Technology SCUT
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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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a proton exchange membrane applied to a direct methanol fuel cell and a preparation method thereof. The method comprises steps of adding porphyrin compound into a Nafion resin solution according to the mass ratio of porphyrin compound to Nafion resin to be 5-50:1000, wherein the porphyrin compound comprises tetraphenyl porphyrin, tetra-sulpho-phenyl porphyrin and tetra-amino-phenyl porphyrin; and carrying out membrane methods such as casting method, pasting method and gumming method on the Nafion resin solution of the porphyrin compound to prepare the modified proton exchange membrane. In the invention, molecules of porphyrin compound, which are not penetrated through methanol and conduct ions are embedded or bonded into the ion channel of a nafion membrane of a perfluorosulfonic membrane by physical or chemical methods to form a structure of hydrogen ion sieve, thereby maintaining higher protons conduction ability and reducing the methanol through rate greatly.

Description

Be applied to proton exchange membrane of direct alcohol fuel battery and preparation method thereof
Technical field
The present invention relates to proton exchange membrane, particularly relate to a kind of modified proton exchange film that is applied to direct alcohol fuel battery and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of electrochemical appliance that can directly chemical energy be converted into electric energy, have effciency of energy transfer height, environmental friendliness, specific energy height (with respect to battery), service temperature low, start fast characteristics, caused that countries in the world extensively pay attention to.Directly be with the liquid alcohol Proton Exchange Membrane Fuel Cells of fuel be commonly referred to as direct alcohol fuel battery (Direct alcohol fuel cell, DAFC).Its outstanding advantage be alcohol rich and easy to get, the low price in source, be easy to carry about with one and store.Compare with general hydrogen-oxygen proton exchange membrane fuel cell simultaneously, directly alcohol fuel battery also has energy density per unit volume height, simple in structure, easy to operate, advantage such as cost is lower, and it represents battery is direct methanol fuel cell (DMFC).The directly extremely favor of industrial community of alcohol fuel battery can be used as the electrical source of power of family's Compact Power Plant, portable electronic appliances power source and electric vehicle etc. in the last few years, had boundless application prospect and huge market.
Proton exchange membrane is the core of direct alcohol fuel battery.At present, widely used perfluorinated sulfonic resin such as Nafion film in hydrogen-oxygen fuel cell when directly being used in alcohol fuel battery, exist serious pure phenomenon of osmosis.The alcohol molecule can arrive negative electrode through proton exchange membrane, causes negative electrode to produce mixed potential on the one hand, reduces the open circuit voltage of DMFC, the utilization ratio of the pure fuel of reduction, causes the loss of fuel; Cathod catalyst is poisoned, cause the oxygen electrode polar to increase significantly, thereby reduce the overall performance of battery, and shortened the work-ing life of DAFC system.Therefore, reducing the rate of permeation of alcohol permeation proton exchange membrane, prepare good, the high performance proton exchange membrane material of the pure ability of resistance, is the important topic of the direct alcohol fuel battery of exploitation high-performance.
Patent CN01133255.7 discloses a kind of preparation method of low methyl alcohol penetrate proton exchange membrane, it embeds metal nano ions such as saturating pure Pd, Pt, Au in the Nafion films, under the prerequisite that does not reduce the membranous electron conductivity of Nafion, reduced methanol permeability.But the use of precious metal has increased the manufacturing cost of film undoubtedly.
It is raw material with the sulfate resin that patent CN200410027559.x discloses a kind of, the proton exchange membrane and the preparation technology thereof that add inorganic nano material, its subject matter is in the loss of inorganic nano material when being difficult to accomplish to reduce methanol crossover with unification that keeps proton conductivity and life-time service.
Cong Pu, Wenhua, Kevin L.Ley, and Eugene S.Smothin discloses and has been entitled as: the proton-conductor composite membrane electrolyte system [J.Electrochem.Soc. of not saturating methyl alcohol, Vol.142, No.7 July 1995]. this system is three layers of electrolyte structure, the not proton conductor of saturating methyl alcohol of densification is clipped in the shape composite structure of three of two-layer dielectric film intermediate formation.The general proton conducting of adopting is Pd or Pt.The methanol permeability of this compound system is little.But this making method complexity makes requiring harshness.
People such as Yoon [J.of Power Sources, 2002,106:215-223] reduce methyl alcohol by the method for modifying dielectric film and pass through, promptly the method by sputter deposits layer of metal Pd on Nafion film surface, but because Nafion film smooth surface, Pd is little at Nafion film surface adhesion force, comes off easily.Therefore must carry out etch processes to Nafion film surface earlier.And it has also reduced proton conductivity when reducing methanol crossover, and cell integrated performance is also had bad influence.
People such as Arico [J.of Power Sources, 2003,123:107-115] adopt vinyl-tetrafluoroethylene to do base material, by the electron beam radiation, and concurrent grafting, and then carry out crosslinked and sulfonation process, make vinyl-tetrafluoroethylene substrate grafting film.Though when reducing methanol crossover, kept certain specific conductivity and battery performance, this method apparatus expensive, operation are too complicated, operate too loaded down with trivial details.
People such as Dimitrova [Solid State Ionics, 2002,150:115-122] adopt Nafion solution and aerosil and phospho-molybdic acid blend, casting film then, and alcohol-resistant performance increases, but its thermostability under the DAFC working conditions is bad.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of when keeping higher proton conductivity, reduce the modified proton exchange film and preparation method thereof of the direct alcohol fuel battery of methanol permeability greatly.
The present invention is by physics or chemical process, can proton conducting but the not porphyrin compound molecule embedding with " hydrogen ion sieve " structure of saturating methyl alcohol or be bonded in the perfluoro sulfonic acid membrane Nafion film, when realizing keeping higher proton conductivity, reduce methanol permeability greatly.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method who is applied to the proton exchange membrane of direct alcohol fuel battery comprises the steps:
(1) mass ratio by porphyrin compound and Nafion resin is 5～50: 1000, and porphyrin compound is added in the Nafion solution; Porphyrin compound comprises tetraphenylporphyrin, four sulfo group phenyl porphyrins, tetrakisaminophenyl porphyrin;
(2) the Nafion resin solution of step (1) gained porphyrin compound is used the film of casting method, coating method and cement-dipping method, made modified proton exchange film.
A kind of modified proton exchange film that is applied to direct alcohol fuel battery is by method for preparing.
The network structure that forms between hydrophobic carbon fluorine main chain district, hydrophilic semi-annular jade pendant acid ion bunch and ion cluster, and the porphyrin compound that is arranged in the ion cluster network structure with hydrogen ion sieve structure; Described hydrogen ion sieve structure is meant the minimum diameter of compound molecule diameter greater than proton conduction passage in the above-mentioned proton exchange membrane, and the N atom at compound molecule center and hydrogen ion interact, and be protonated fast in acidic solution, with solution exchange hydrogen ion.
Nafion film of the present invention is that the polytetrafluoroethylene (PTFE) skeleton is connected with-SO by ehter bond from molecular level 3The long side chain (structural formula is seen Fig. 1) of H group end capping, wherein, k, m, n are the positive integer greater than 10.Hydrophilic-SO 3H group suction back forms successive proton transport passage, and hydrophobic main chain prevents that then the excessive swelling of film is to guarantee the stable of film pattern and size.
As shown in Figure 2, the structure of Nafion film mainly comprises the network structure that forms between hydrophobic carbon fluorine main chain district (polymer parent), hydrophilic ion cluster (ionic group aggregate) and ion cluster.For the Nafion film of complete wetting, the diameter of ion cluster is about 4nm, and the spacing between ion cluster is about 5nm.The network structure that forms between ion cluster is unique passage of interior ion of film and water molecules migration.The diameter of this passage is about 1nm.
Porphyrin compound with " hydrogen ion sieve " structure comprises tetraphenylporphyrin, four sulfo group phenyl porphyrins, tetrakisaminophenyl porphyrin.Have following characteristics: one, the compound molecule diameter is greater than the minimum diameter of proton conduction passage in the above-mentioned proton exchange membrane; Two, the compound molecule center has ring texture, have in this structure can with the interactional atom of hydrogen ion, can be protonated fast in acidic solution, with solution exchange hydrogen ion.With tetraphenylporphyrin (TPPH 4) be example, (TPPH in acidic solution 4 2+), because the quick exchange effect of H atom and solution proton in the ring, its sterie configuration plane macromole ring structure, substituted benzene ring diagonal with it center, its substituted benzene ring center is about 1.287nm apart, apart two H atoms farthest are at a distance of about 1.786nm, the maximum area of " sieve aperture " that is surrounded by 4 H atoms is about 0.271nm * 0.240nm, and the effective vanderwaals radius of H atom is 0.110-0.120nm, consider the vanderwaals effect and the electrostatic interaction that may exist between the adjacent H atom, comprise methyl alcohol, water molecules other interior polyatomic molecule be difficult to by.
As shown in Figure 3, the modified proton exchange film that the porphyrin compound molecule that will have " hydrogen ion sieve " structure 1 makes after embedding or be bonded in the ion cluster 2 of perfluoro sulfonic acid membrane, utilize its molecule space steric effect to reduce methanol permeability, the quick exchange of H atom and solution proton is used for the conducting proton in encircle in acidic solution by it simultaneously, can realize that reduction methanol permeability and maintenance are than the unification of high proton conductivity in the proton exchange membrane.
The modified proton exchange film preparation method of low methyl alcohol penetrate of the present invention is to be raw material with commercially available perfluorinated sulfonic resin, add porphyrin compound, prepare modified proton exchange film by comprising films such as casting method, coating method and cement-dipping method with " hydrogen ion sieve " structure.
Compared with the prior art, the present invention has following beneficial effect: the modified proton exchange film of the present invention's preparation is when realizing keeping higher proton conductivity, reduce methanol permeability greatly, make proton exchange membrane be more suitable for being applied to direct alcohol fuel battery through modification.
Description of drawings
Fig. 1 is the chemical structure of Nafion film.
Fig. 2 is the structural representation of Nafion film intermediate ion bunch and ionic channel.
Fig. 3 is a modified proton exchange film membrane structure synoptic diagram.
Embodiment
For better understanding the present invention, the present invention is described further below in conjunction with drawings and Examples, but the scope of protection of present invention is not limited to the scope that embodiment is represented.
Embodiment 1: in Nafion resin solution (DE-520, E.I.Du Pont Company produce), add tetraphenylporphyrin by the ratio of Nafion portions of resin tetraphenylporphyrin=1: 0.005, stir casting film-forming on the sheet glass of cleaning afterwards.Dry postcooling down at 60 ℃ and to room temperature, take off film.With the film taken off at 1M H 2SO 4Soak 24h in the aqueous solution.Be immersed in the deionized water stand-by after the taking-up washing.Obtain tetraphenylporphyrin modification Nafion film.
Embodiment 2: in Nafion resin solution (DE-520), press Nafion portions of resin tetraphenylporphyrin=1: 0.01 adding tetraphenylporphyrin, stir back casting film-forming on the sheet glass of cleaning.Dry postcooling down at 60 ℃ and to room temperature, take off film.With the film taken off at 1M H 2SO 4Soak 24h in the aqueous solution.Be immersed in the deionized water stand-by after the taking-up washing.Obtain tetraphenylporphyrin modification Nafion film.
Embodiment 3: in Nafion resin solution (DE-520), add tetraphenylporphyrin in the ratio of Nafion portions of resin tetraphenylporphyrin=1: 0.05, stir back casting film-forming on the sheet glass of cleaning.Dry postcooling down at 60 ℃ and to room temperature, take off film.With the film taken off at 1MH 2SO 4Soak 24h in the aqueous solution.Be immersed in the deionized water stand-by after the taking-up washing.Obtain tetraphenylporphyrin modification Nafion film.
Embodiment 4: in Nafion resin solution (DE-520) solution, press Nafion portions of resin four p-sulfonic acid base phenyl porphyrins=1: 0.01 adding four p-sulfonic acid base phenyl porphyrin, stir back casting film-forming on the sheet glass of cleaning.Dry postcooling down at 60 ℃ and to room temperature, take off film.With the film taken off at 1M H 2SO 4Soak 24h in the aqueous solution.Be immersed in the deionized water stand-by after the taking-up washing.Obtain four p-sulfonic acid base phenyl porphyrin modification Nafion films.
Embodiment 5: in Nafion resin solution (DE-520) solution, press Nafion portions of resin tetraphenylporphyrin=1: 0.01 adding tetrakisaminophenyl porphyrin, stir back casting film-forming on the sheet glass of cleaning.Dry postcooling down at 60 ℃ and to room temperature, take off film.With the film taken off at 1M H 2SO 4Soak 24h in the aqueous solution.Be immersed in the deionized water stand-by after the taking-up washing.Obtain tetrakisaminophenyl porphyrin modification Nafion film.
The present invention (as embodiment 2, other implementation result basically identicals) preparation be doped with 1%TPPH 4 2+Nafion, the proton exchange membrane of undoped (Nafion117) then is transparent khaki color.Its proton conductivity is respectively 8.7 * 10 -3S/cm and 8.5 * 10 -3S/cm, methanol permeability is respectively 4.7 * 10 -7Cm 2/ s and 8.9 * 10 -7Cm 2/ s.Testing method: proton conductivity adopts the proton conductivity of two electrode AC impedance methods test proton exchange membrane.The high resolving power gas-chromatography of passing through of methanol permeability compares.

Claims (3)

1. a preparation method who is applied to the proton exchange membrane of direct alcohol fuel battery is characterized in that comprising the steps:
(1) mass ratio by porphyrin compound and Nafion resin is 5～50: 1000, and porphyrin compound is added in the Nafion solution; Porphyrin compound comprises tetraphenylporphyrin, four sulfo group phenyl porphyrins, tetrakisaminophenyl porphyrin;
(2) the Nafion resin solution of step (1) gained porphyrin compound is used the film of casting method, coating method and cement-dipping method, made modified proton exchange film.
2. a modified proton exchange film that is applied to direct alcohol fuel battery is characterized in that it is by the described method preparation of claim 1.
3. the modified proton exchange film that is applied to direct alcohol fuel battery according to claim 2, it is characterized in that: the network structure that forms between hydrophobic carbon fluorine main chain district, hydrophilic semi-annular jade pendant acid ion bunch and ion cluster, and the porphyrin compound that is arranged in the ion cluster network structure with hydrogen ion sieve structure; Described hydrogen ion sieve structure is meant the minimum diameter of compound molecule diameter greater than proton conduction passage in the above-mentioned proton exchange membrane, and the N atom at compound molecule center and hydrogen ion interact, and be protonated fast in acidic solution, with solution exchange hydrogen ion.
CN2010105267754A 2010-10-30 2010-10-30 Proton exchange membrane applied to direct methanol fuel cell and preparation method thereof Pending CN102002167A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108630972A (en) * 2018-03-14 2018-10-09 上海博暄能源科技有限公司 A kind of preparation method of the quantum-dot modified proton exchange membrane of oxidation-resistant graphite alkene
CN108923055A (en) * 2018-05-17 2018-11-30 上海博暄能源科技有限公司 A kind of preparation method of the modified perfluoro sulfonic acid membrane of big ring conjugated complex
CN113563350A (en) * 2021-06-24 2021-10-29 浙江工业大学 Compound with porphyrin structure and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101467291A (en) * 2006-06-14 2009-06-24 约翰逊马西有限公司 Ion-conducting membrane

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101467291A (en) * 2006-06-14 2009-06-24 约翰逊马西有限公司 Ion-conducting membrane

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108630972A (en) * 2018-03-14 2018-10-09 上海博暄能源科技有限公司 A kind of preparation method of the quantum-dot modified proton exchange membrane of oxidation-resistant graphite alkene
CN108630972B (en) * 2018-03-14 2021-08-06 上海博暄能源科技有限公司 Preparation method of antioxidant graphene quantum dot modified proton exchange membrane
CN108923055A (en) * 2018-05-17 2018-11-30 上海博暄能源科技有限公司 A kind of preparation method of the modified perfluoro sulfonic acid membrane of big ring conjugated complex
CN113563350A (en) * 2021-06-24 2021-10-29 浙江工业大学 Compound with porphyrin structure and preparation method and application thereof
CN113563350B (en) * 2021-06-24 2022-05-24 浙江工业大学 Compound with porphyrin structure and preparation method and application thereof

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Application publication date: 20110406