CN1268017C - Method of lowering permeability of proton exchange film methy alcohol contg fluorine sulfonic acid - Google Patents
Method of lowering permeability of proton exchange film methy alcohol contg fluorine sulfonic acid Download PDFInfo
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- CN1268017C CN1268017C CNB2004100609459A CN200410060945A CN1268017C CN 1268017 C CN1268017 C CN 1268017C CN B2004100609459 A CNB2004100609459 A CN B2004100609459A CN 200410060945 A CN200410060945 A CN 200410060945A CN 1268017 C CN1268017 C CN 1268017C
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Abstract
The present invention relates to a method for reducing the methanol permeability of fluoride bearing sulfoacid type proton exchange membranes, which comprises the steps that ammonium cation polymers and reducing agents are adopted to reduce Pd salt in water solution to synthesize cationized nanometer Pd particles, a fluoride bearing sulfoacid type proton exchange membrane is put into water dispersion fluid of the cationized nanometer Pd particles to be soaked, and through electrostatic self-assembly, and the Pd particles are assembled on inlets and outlets of sulfonic acid radical groups forming methanol permeability channels on the proton exchange membrane, so that the permeability of methanol to the membrane is reduced. If the method is adopted, the carrying capacity of noble metal Pd is small (1 to 6.8 micro g/cm<2>), the cost of methanol resistance is low, and simultaneously, the proton conducting capability of membrane is basically not influenced.
Description
Technical field
The invention belongs to a kind of method that reduces sulfonic fluoropolymer type proton exchange membrane methanol permeability.
Background technology
In today that global energy crisis and environment go from bad to worse, improve resource utilization, reduce the important topic that environmental pollution has become scientific research.Fuel cell technology has become one of focus of international new and high technology competition as a kind of energy technology of cleaning.Direct methanol fuel cell (DMFC) is owing to the methyl alcohol source is enriched, is easy to carry and store, can realize the extremely favors of industrial circle of advantage such as zero discharge or low emission.In DMFC, at present widely used is the sulfonic fluoropolymer type proton exchange membrane that chemical stability is better, proton conductivity is higher, but the hydrophobic property of the fluorine-containing main chain of this film macromolecule and sulfonate radical is existed with the cluster form of hollow as the water-wet behavior of the sulfonate radical side chain of proton conducting group, the continuous structure with proton conducting of this cluster has very high permeability [J.Power Sources 2002 to methyl alcohol, 112,339; J.Electrochem.Soc.2004,151, A413].After the methyl alcohol penetrate proton exchange membrane, not only produce mixed potential at oxygen electrode, cause the cathod catalyst poisoning, cause cathodic polarization to increase, battery performance reduces, and the methyl alcohol unreacted that sees through is directly discharged from battery, fuel but also contaminated environment had not only been wasted, so methanol permeation becomes one of key issue of restriction direct methanol fuel cell industrialization, and [J.Power Sources 1999,84,70; J.Electrochem.Soc.2004,151, A413].
In order to solve the infiltration methyl alcohol problem of DMFC, the researcher is exploring the resistance alcohol dielectric film of synthesizing new, United States Patent (USP) 6,759 always, 157 provide a kind of proton exchange membrane of method preparation resistance alcohol of poly phosphazene doping oxyacid, adopt the composite membrane conductivity and the Nafion of this method preparation
(a kind of sulfonic fluoropolymer type proton exchange membrane that Du Pont company produces) is similar, and methanol permeability is the latter's 1/5; Chinese patent application number 02115185.7,02115186.5 has proposed the method that a kind of polystyrene sulfonate film is used for methanol fuel cell, the membrane conductivity and the Nafion of their preparation
Film is close, and methanol permeability is Nafion when identical thickness
Film～1/2; Its alcohol-rejecting ability is excellent more after mixing inorganic nano-particle, is Nafion
Film～1/5 (Chinese patent application number 02115184.9).
Yet consideration for proton exchange membrane dimensional stability and chemical stability, people still tend to use sulfonic fluoropolymer type proton exchange membrane in direct methanol fuel cell, modification is a kind of more promising method to sulfonic fluoropolymer type proton exchange membrane, one of method of modification is that employing polytetrafluoroethylene (PTFE) perforated membrane is the composite membrane of matrix, dipping perfluorinated sulfonic resin, United States Patent (USP) 5,795,668 adopt the composite membrane conductivity and the Nafion of this method preparation
Similar, methanol permeability has the decline less than an order of magnitude; United States Patent (USP) 6,447,943 on the basis of this method further doping inorganic nano-particle, methanol permeation drops to～20mA/cm
2(calculating) with the oxidization of methanol electric current.Two of the method for modification is that the sulfonic fluoropolymer film is carried out physics is compound, and methanol permeability descends generally less than two orders of magnitude when adopting this method, and is accompanied by the decline of membrane conductivity.As PuC. etc. the not proton conductor of saturating methyl alcohol of one deck densification is clipped in two-layer Nafion
Form composite electrolyte membrane between the film, but because the increase of the binding film thickness between the different layers sharply descends the proton conducting performance of dielectric film [J.electrochem.Soc., 1995,142,119].It is a kind of relatively more good processing method that the Pd that employing has a proton conductivity carries out chemical modification as decorative material to sulfonic fluoropolymer type proton exchange membrane, [J.power sources such as Choi Won, 2001,96,411～414], [J.Membrane Sci. such as Z.Q.Ma, 2003,215,327～336] and [J.powersources, 2002 such as S.R.Yoon, 106,215～423] adopt sputtering method at Nafion
Film surface deposition layer of metal palladium or palldium alloy reduce methyl alcohol penetrate, successfully make the transmitance of methyl alcohol be reduced to half of pure film, but this method exist palladium and Nafion
Film is in conjunction with shortcoming such as insecure and palladium consumption is excessive; [Electrochem.Commn., 2003,5,571～574] such as Young-Min Kim adopt the method for nano metal Pd particle deposition to synthesize alcohol-barrier proton exchange film, in their research, soak the Nafion that Pd solution is arranged
Film is by NaBH
4Thereby reduction embedding nano metal Pd particle in film internal water passage, the result shows, handles back Nafion
The ability of infiltration methyl alcohol only be 1/8 before handling, but the conductivity of film has 25% decline.
Summary of the invention
The objective of the invention is to overcome the high shortcoming of sulfonic fluoropolymer type proton exchange membrane methanol permeability, a kind of conductivity height, methanol crossover is low, processing cost the is low direct methanol fuel cell resistance alcohol processing method with proton exchange membrane is provided.Be a kind of method that reduces sulfonic fluoropolymer type proton exchange membrane methanol permeability.
The thinking of this method is: cationic polymer modified Pd particle static is self-assembled to the outlet and the inlet of sulphur radical family of the formation methanol crossover passage on proton exchange membrane surface, thereby reduce the permeability of methyl alcohol to proton exchange membrane.Processed proton exchange membrane must be that proton conductive group is a sulfonate radical, and the high polymer main chain in the film is fluorine-containing proton exchange membrane partly or entirely, as the Nafion of DuPont company
The Aciplex of series membranes, Asahi Chemical company
The Flemion of series membranes, AsahiGlass company
The Dow of series membranes, Dow Chemical
Film, the sulfonic fluoropolymer type proton exchange membrane that the BAM film of Ballard company and other meet this feature; The cationic polymer of choosing can not enter proton exchange membrane inside the proton conductivity of film is exerted an influence, the cationic polymeric molecule chain length should be greater than the diameter of the crystalline phase hydrophobic region passage that does not have the sulfonate radical side chain in the proton exchange membrane, but less than the diameter of sulfonate radical cluster; With selected cationic polymer is modified ion, reduction Pa salt is with the nanometer Pa particle of synthesizing cationicization in the aqueous solution, nanometer Pa grain diameter also should be greater than the diameter of the crystalline phase hydrophobic region passage that does not have the sulfonate radical side chain in the proton exchange membrane, but diameter less than the sulfonate radical cluster, cationic polymer and Pd particle just can not enter proton exchange membrane inside the proton conductivity of film is exerted an influence like this, after the activation of sulfonic fluoropolymer type proton exchange membrane cleaning, the aqueous dispersions of putting into the cationization nanometer Pd particle that makes soaks with static self assembly Pd particle, to reduce sulfonic fluoropolymer type proton exchange membrane methanol permeability.
The concrete grammar step is
Step 1: select ammonium cationoid polymer and reducing agent for use, the nano metal Pd particle of reduction Pd salt synthesizing cationicization in the aqueous solution, reducing agent is selected strong reductant NaBH for use
4, N
2H
2H
2O and H
2In any; Or select in weak reductant methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol any for use, synthesis condition when adopting strong reductant is: the mol ratio of cationic polymer and nano metal Pd salt is 1～8: 1, the mol ratio of reducing agent and Pd salt is 1～4: 1, solvent is the deionized water of conductivity＞18M Ω, the pH of reduction system＞7 are with N
2Be protection gas; Adopt the synthesis condition of weak reductant to be: the mol ratio of cationic polymer and nano metal Pd salt is 1～8: 1, solvent is the deionized water of conductivity＞18M Ω, and the mass ratio of reducing agent and water is 2: 3, and reduction temperature is 70～84 ℃, the pH of reduction system＞7 are with N
2Be protection gas; Described ammonium cationoid polymer is selected from any of copolymer, poly diallyldimethylammonium chloride of PDDA, acrylamide-dimethyl diallyl ammonium chloride;
Step 2: with sulfonic fluoropolymer type proton exchange membrane successively at the H of 5wt%
2O
2, deionized water, 1mol/L H
2SO
4, and deionized water in respectively soak 30 minutes after, the aqueous dispersions of putting into the prepared cationization nanometer of step 1 Pd soaked 10～50 hours, by the electrostatic attraction self-assembled nanometer Pd particle between the azochlorosulfonate acid anion on the cation that is modified at the Pd particle surface and proton exchange membrane surface, make that the carrying capacity of Pd reaches 1～6.8 μ g/cm on the film
2
Step 3: with the resulting self assembly of step 2 proton exchange membrane of nanometer Pd particle successively at the H of 1mol/L
2SO
4With respectively soaked in the deionized water 30 minutes, promptly obtain the sulfonic fluoropolymer type proton exchange membrane that methanol permeability has reduced.
Described sulfonic fluoropolymer type proton exchange membrane is the Nafion of DuPont company
The Aciplex of film, Asahi Chemical company
The Flemion of film, Asahi Glass company
The Dow of film, Dow Chemical
Film, the BAM film of Ballard company.
Described ammonium cationoid polymer is selected from any of copolymer, poly diallyldimethylammonium chloride of PDDA, acrylamide-dimethyl diallyl ammonium chloride.
In order to guarantee the complete of reduction reaction, selected reducing agent consumption waits dosage in the required theoretical chemistry dose value of reduction Pd salt at least, and it is excessive to be generally.
The present invention is by regulating ammonium cationoid polymer and the ratio of Pd and the pH value of reduction system, can regulate the Pd particle grain size: PDDA (PDDA) is big more with the molar ratio of Pd, the Pd grain diameter is more little, is generally 1～8: 1 (referring to accompanying drawing 1); The pH value is high more, and the Pd grain diameter is more little, general pH＞7 (referring to accompanying drawing 2).
By change the carrying capacity that time that film soaks can change Pd in the nanometer Pd of cationization dispersion liquid, the high methanol permeability is more little more for the Pd carrying capacity, but the Pd carrying capacity has a peak, the all sulfonate group in film surface are all occupied by the nanometer Pd particle of cationization when reaching this value, and this moment, the Pd carrying capacity was slightly less than the carrying capacity～6.8 μ g/cms of nanometer Pd particle when the tight arrangement in film surface
2(slight variations being arranged with nanometer Pd particle diameter difference), the time that reaches this amount was generally 10～50 hours, can measure by the uv-visible absorption spectroscopy of film.Adopt preparation condition of the present invention, year nanometer Pd particle carrying capacity on film surface is 1～2.2 μ g/cm
2
The present invention compares with existing method, has following advantage:
1, resistance alcohol is handled and is had the accuracy of molecular scale, because mutual electrostatic force between sulfonate group and the cation, cation modified nanometer Pd particle can be assembled on the sulfonate radical cluster on proton exchange membrane surface exactly, promptly forms the outlet and the inlet of methanol crossover.The sulfonate radical cluster is local just can be assembled into nanometer Pd particle owing to have on the film surface, and does not have the place of sulfonate radical cluster just can not assemble nanometer Pd particle, and it is very high therefore to hinder pure efficient, can reduce by 6～9 orders of magnitude.
2, since the diameter of synthetic nanometer Pd particle and cationic polymer all greater than the diameter of the crystalline phase hydrophobic region passage that does not have the sulfonate radical side chain in the proton film, but diameter less than the sulfonate radical cluster, assembling back nanometer Pd particle is present in the sulfonate radical cluster on film surface, and nanometer Pd particle and cationic polymer can not enter the inside of film; And because the special atomic arrangement mode of Pd can allow H
+Move freely, therefore assembling does not have loss substantially to the conductivity of proton exchange membrane, and the conductivity of film is very high.
3, because nanometer Pd particle only is assembled into the place that there is the sulfonate radical cluster on the film surface, and be the individual layer assembling of nanometer Pd particle, so the assembling amount of Pd is less than 6.8 μ g/cm
2, cost is low.
In sum, the sulfonic fluoropolymer type proton exchange membrane that this method is handled has conductivity height, methanol permeability is low, the noble metal carrying capacity is few and cost is low characteristics, and wide application prospect is arranged in direct methanol fuel cell.
Description of drawings
The relation curve of the mol ratio of Fig. 1 ammonium cationoid polymer-PDDA (PDDA) and Pd salt and the Pd nano particle diameter that obtains
The relation curve of Fig. 2 reduction system pH value and the Pd nano particle diameter that obtains
Figure is by finding out, the mol ratio of cationic polymer and Pd is larger, and the Pd particle is less, and reduction system pH value is higher, and the Pd grain diameter is less.
Embodiment
Following embodiment further specifies of the present invention.
Embodiment 1:Nafion
The resistance alcohol of 117 films is handled
1, choose the cationic polymer of strand length at 1～4nm, the PDDA (PDDA) of average molecular weight Mw～2000 is the cationic polymer of decorated nanometer Pd.
2, getting concentration is that the PDDA solution 10mL of 0.005mol/L adopts the deionized water dilution of conductivity＞18M Ω to be 79mL, adds the PdCl that concentration is 0.05mol/L successively
2Solution 1mL, isopropyl alcohol 60mL mixes, and regulating mixed solution pH value is 8.5, N
2Warming-in-water to 75 ℃ reaction is 10 minutes under the protection, obtains the nanometer Pd particle of cationization, and grain diameter is～2nm.
3,4 Nafion
117 films are successively at the H of 5wt%
2O
2, deionized water, 1mol/L H
2SO
4, respectively soak 30 minutes in the deionized water after, the nanometer Pd dispersion liquid of putting into the cationization that step 2 makes soaks with static self assembly Pd particle, gets assembling 0,10,30,40 little up-to-date styles, successively at the H of 1mol/L
2SO
4, respectively soak the resistance alcohol Nafion117 proton exchange that has obtained assembling nanometer Pd particle after 30 minutes in the deionized water and touch, its Pd carrying capacity, conductivity and methanol crossover amount (methanol concentration is 2mol/L, and infiltration capacity is calculated with the potentiostatic deposition electric current) are as shown in table 1.
Nafion after the self assembly of table 1 different time
The performance parameter of 117 films
| The self assembly time (hour) | Pd carrying capacity (μ g/cm 2) | Conductivity (S/cm) | Methanol crossover amount (A/cm 2) |
| 0 (pure film) 10 hours 30 hours 40 hours | 0.00 0.93 1.59 1.62 | 0.112 0.110 0.111 0.112 | 6.0*10 -2 5.2*10 -5 9.6*10 -8 2.3*10 -10 |
Embodiment 2:Dow
The resistance alcohol of film is handled
1, select for use the copolymer of average molecular weight Mw～1000 acrylamides-dimethyl diallyl ammonium chloride to be decorated nanometer Pd cationic polymer.
2, get the acrylamide that concentration is 0.001mol/L-dimethyl diallyl ammonium chloride copolymer solution 80mL, with 1mL concentration be the PdCl of 0.05mol/L
2Mix, regulating mixed solution pH value is 8, N
2Protection is the NaBH of 1mol/L with the speed dropping concentration of 1mL/min down
4Solution 0.2mL (surpass dosage 3 times, also can wait dosage) obtains the nanometer Pd particle of cationization, and grain diameter is～1.6nm.
3,4 Dow
Film is successively at the H of 5wt%
2O
2, deionized water, 1mol/L H
2SO
4, respectively soak 30 minutes in the deionized water after, the nanometer Pd dispersion liquid of putting into the cationization that step 2 makes soaks with static self assembly Pd particle, gets assembling 0,10,20,40 little up-to-date styles, successively at the H of 1mol/L
2SO
4, respectively soak the resistance alcohol Dow proton exchange that has obtained assembling nanometer Pd particle after 30 minutes in the deionized water and touch, its Pd carrying capacity, conductivity and methanol crossover amount (methanol concentration is 2mol/L, and infiltration capacity is with the potentiostatic deposition galvanometer) are as shown in table 2.
Dow after the self assembly of table 2 different time
The film properties parameter
| The self assembly time (hour) | Pd carrying capacity (μ g/cm 2) | Conductivity (S/cm) | Methanol crossover amount (A/cm 2) |
| 0 (pure film) 10 hours 30 hours | 0.00 1.02 1.89 | 0.114 0.113 0.115 | 8.4*10 -2 1.2*10 -4 4.5*10 -8 |
| 40 hours 50 hours | 2.14 2.16 | 0.113 0.113 | 6.3*10 -10 4.6*10 -10 |
Embodiment 3: the resistance alcohol of Kynoar grafted polystyrene sulfonate resin film is handled
To pressing the Kynoar grafted polystyrene sulfonate resin film forming of the described method preparation of CN1330425A, the processing of thickness 85um.Treatment step is:
1, the poly diallyldimethylammonium chloride of choosing average molecular weight Mw～1000 is the cationic polymer of decorated nanometer Pd.
2, getting concentration is that the tetramethyl ammonium chloride solution 10mL of 0.005mol/L adopts the deionized water dilution of conductivity＞18M Ω to be 79mL, adds the PdCl that concentration is 0.05mol/L successively
2Solution 1mL, absolute ethyl alcohol 60mL mixes, and regulating mixed solution pH value is 12, N
2Warming-in-water to 84 ℃ reaction is 10 minutes under the protection, obtains the nanometer Pd particle of cationization, and grain diameter is～1.3nm.
3,4 polyvinylidene fluoride films are successively at the H of 5wt%
2O
2, deionized water, 1mol/L H
2SO
4, respectively soak 30 minutes in the deionized water after, the nanometer Pd dispersion liquid of putting into the cationization that step 2 makes soaks with static self assembly Pd particle, gets assembling 0,10,20,40 little up-to-date styles, successively at the H of 1mol/L
2SO
4, respectively soak the resistance alcohol proton exchange that has obtained assembling nanometer Pd particle after 30 minutes in the deionized water and touch, its Pd carrying capacity, conductivity and methanol crossover amount (methanol concentration is 2mol/L, and infiltration capacity is with the potentiostatic deposition galvanometer) are as shown in table 3.
Polyvinylidene fluoride film performance parameter after the self assembly of table 3 different time
| The self assembly time (hour) | Pd carrying capacity (μ g/cm 2) | Conductivity (S/cm) | Methanol crossover amount (A/cm 2) |
| 0 (pure film) 10 hours 30 hours 40 hours | 0.00 0.98 1.63 1.72 | 0.045 0.045 0.043 0.044 | 6.2*10 -3 3.7*10 -5 2.6*10 -9 3.5*10 -10 |
Claims (2)
1, a kind of method that reduces sulfonic fluoropolymer type proton exchange membrane methanol permeability is characterized in that method step is:
Step 1: select ammonium cationoid polymer and reducing agent for use, the nano metal Pd particle of reduction Pd salt synthesizing cationicization in the aqueous solution, reducing agent is selected strong reductant NaBH for use
4, N
2H
2H
2O and H
2In any; Or select in weak reductant methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol any for use, synthesis condition when adopting strong reductant is: the mol ratio of cationic polymer and nano metal Pd salt is 1～8: 1, the mol ratio of reducing agent and Pd salt is 1～4: 1, the pH of reduction system＞7, solvent is the deionized water of conductivity＞18M Ω, with N
2Be protection gas; Adopt the synthesis condition of weak reductant to be: the mol ratio of cationic polymer and nano metal Pd salt is 1～8: 1, the mass ratio of reducing agent and water is 2: 3, and reduction temperature is 70～84 ℃, the pH of reduction system＞7, solvent is the deionized water of conductivity＞18M Ω, with N
2Be protection gas; Described ammonium cationoid polymer is selected from any of copolymer, poly diallyldimethylammonium chloride of PDDA, acrylamide-dimethyl diallyl ammonium chloride;
Step 2: with sulfonic fluoropolymer type proton exchange membrane successively at the H of 5wt%
2O
2, deionized water, 1mol/L H
2SO
4After respectively soaking 30 minutes in the deionized water, the aqueous dispersions of putting into the prepared cationization nano metal of step 1 Pd particle soaked 10～50 hours, by the electrostatic attraction self-assembled nanometer Pd particle between the azochlorosulfonate acid anion on the cation that is modified at the Pd particle surface and proton exchange membrane surface to making the Pd carrying capacity on the film reach 1～6.8 μ g/cm
2
Step 3: with the resulting self assembly of step 2 proton exchange membrane of nanometer Pd particle successively at the H of 1mol/L
2SO
4With respectively soaked in the deionized water 30 minutes, obtain the sulfonic fluoropolymer type proton exchange membrane that methanol permeability has reduced.
2, the method for claim 1 is characterized in that described sulfonic fluoropolymer type proton exchange membrane is the Nafion of DuPont company
The Dow of 117 films, Dow Chemical
Film and Kynoar grafted polystyrene sulfonate resin film.
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|---|---|---|---|
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|---|---|---|---|
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| CN1268017C true CN1268017C (en) | 2006-08-02 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100452501C (en) * | 2006-06-22 | 2009-01-14 | 厦门大学 | Modified alcohol-barrier proton exchange film based on hydrophilic area surface and its production |
| CN100444438C (en) * | 2007-03-01 | 2008-12-17 | 上海交通大学 | A method for improving the carbinol-resisting infiltration of fluorine-containing sulfonic acid proton exchange film |
| US7897691B2 (en) * | 2008-05-09 | 2011-03-01 | Gm Global Technology Operations, Inc. | Proton exchange membranes for fuel cell applications |
| CN102618858B (en) * | 2012-04-05 | 2014-05-07 | 哈尔滨工业大学 | Methanol-blocking modified preparation method of Pd-Nafion composite membrane |
| CN205122696U (en) * | 2015-11-19 | 2016-03-30 | 广州道动新能源有限公司 | Novel proton exchange membrane for methanol fuel cell |
| CN112151819A (en) * | 2020-09-12 | 2020-12-29 | 厦门晋简新能源科技有限公司 | Battery slurry and using method thereof |
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