CN1750293A - Modified proton exchange film capable of reducing alcohol permeation and its preparing method and use - Google Patents
Modified proton exchange film capable of reducing alcohol permeation and its preparing method and use Download PDFInfo
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- CN1750293A CN1750293A CNA2005100341327A CN200510034132A CN1750293A CN 1750293 A CN1750293 A CN 1750293A CN A2005100341327 A CNA2005100341327 A CN A2005100341327A CN 200510034132 A CN200510034132 A CN 200510034132A CN 1750293 A CN1750293 A CN 1750293A
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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
This invention discloses a preparation method for reducing the penetration rate for a modified proton exchange film by alcohol including the following steps: 1, pretreatment of the proton exchange film, 2, depositing PAn at the proton exchange film. This invention only takes aniline monomers as the raw material, which is easy and the process for treating the Nafion 117 film is convenient not necessary for any special equipments. The penetration rate of alcohol for the Nafion 117 film is reduced greatly after being processed by PAn, yet the proton conductivity reduces a little.
Description
Technical field
The present invention relates to a kind of novel modified proton exchange film capable of reducing alcohol permeation and its preparation method and use.
Background technology
Fuel cell be a kind of peace and quiet, cleaning, flexibly, reliably, generation technology efficiently because the numerous advantage of fuel cell more and more is subject to people's attention, have broad application prospects.
The fuel cell optimum fuel is a hydrogen, but because the hydrogen fuel poor safety performance, is difficult for transportation and is transformed into gas station by original gas station costly, will more help applying of fuel cell so liquid fuel replaces pure hydrogen to act as a fuel.In numerous liquid fuels, methyl alcohol is abundant because of originating, cheap, be easy to carry about with one and storage, advantage such as environmentally friendly, becomes the desirable fuel of fuel cell.Direct methanol fuel cell (DMFC) does not need reformer apparatus, directly be fuel with methyl alcohol, make the electricity generation system simplicity, miniaturization and, can be used in the future vehicle power and removable power supply, thereby be the research focus of current fuel cell field, but methyl alcohol seriously is to influence one of DMFC practicability subject matter by the proton exchange membrane infiltration, the problem that therefore solves methanol crossover is the hot topic of studying now.
(SHAO Zhi-Gang such as Shao Zhi-Gang, WANG Xin, HSING I M.Journal of MembraneScience, 2002,210:147-153.) combination film structure that adopted three-layer sandwich type is attached to the two sides of Nafion film with polyvinyl ethanol (PVA) and the hybrid films of Nafion, again it carried out chemical crosslinking and sulfonation.In the hybrid films of PVA and Nafion film, PVA has alcohol-rejecting ability preferably, the Nafion film then has proton conductivity preferably, when the mass ratio of PVA and Nafion is 1: 1, hybrid films has the highest α value (definition α is the optionally ratio of hybrid films and Nafion film in the literary composition), hybrid films has been carried out crosslinked and sulfonation, and record the α value and increase this moment.
(KIM Y S such as Yu Seung Kim, HICKNER M A, DONG L, et a1.Journal of MembraneScience, 2004,243:317-326.) having synthesized sulfonation poly (arylene ether) sulfone (BPSH), this polymer has two kinds of microscopic patterns, and a kind of is enclosed construction: promptly hydrophilic parts is partly isolated by a series of hydrophobic group; Another kind of is Open architecture: promptly hydrophilic parts is in contact with one another, or even couples together.Wherein enclosed activation energy higher (20KJ/mol), open activation energy lower (15KJ/mol), and the methanol permeability of enclosed BPSH is more much smaller than open BPSH.In addition, the selectivity of enclosed polymer (proton conductivity/methanol permeability) increases along with the increase of sulfonation degree, and the selectivity of open polymer then reduces along with the increase of sulfonation degree.Compare with the Nafion117 film, this polymer has lower methanol permeability and higher selectivity.
(GIL M such as Maria Gil, JI Xiang-ling, LI Xian-feng, et al.Journal of Membrane Science, 2004,234:75-81.) method with direct polymerization sulfonated monomer has obtained sulfonated polyether-ether-ketone (S-PEEK), because S-PEEK does not have tangible hydrophobic region and hydrophilic area, and polymer backbone has little pliability, makes this film that alcohol-resistant performance preferably be arranged.In the time of 25 ℃, the methyl alcohol diffusion coefficient of S-PEEK film is 3 * 10
-7Cm
2/ S to 5 * 10
-8Cm
2/ S is than 2 * 10 of Nafion film
-6Cm
2/ S has reduced an order of magnitude.The proton conductivity of S-PEEK film increases along with the rising of sulfonation degree and temperature, and when sulfonation degree was 1.1, its conductivity was close with the Nafion film.
The alternative membrane of the Modified Membrane of said method gained and Nafion film all is better than the Nafion film in resistance aspect pure, but the proton exchange membrane in the DMFC membrane electrode is still used the Nafion film now, this be since their combination property not as the Nafion film.Such as the preparation process more complicated of alternative membrane, some alternative membrane is not so good as the Nafion film at aspects such as thermostability energy, mechanical performance or acidproof abilities.The conductive polymer thing is owing to there is well thermally-stabilised and chemical stability, and advantage such as good electrochemical, is to study focus at present.Polyaniline is owing to having higher conductivity, the stability to oxygen and water, easy synthetic method, the convenience of mixing, good electrochemical stability performance to be considered to most promising electricity and to lead macromolecular material.Therefore electro-deposition polyaniline on the Nafion film both can stop methanol crossover, can help the assembling of membrane electrode again.
Summary of the invention
The objective of the invention is to provides a kind of novel modified proton exchange film capable of reducing alcohol permeation at overcoming the shortcoming that prior art exists.
Another object of the present invention is to provide the preparation method of modified proton exchange film.
A further object of the invention is this modified proton exchange film is applied on the direct methanol fuel cell.
To achieve the above object of the invention, the present invention has taked following technical scheme:
A kind of preparation method of modified proton exchange film capable of reducing alcohol permeation comprises following technical step:
(1) preliminary treatment of proton exchange membrane: the H that proton exchange membrane is put into 2～5% weight
2O
2Boiled in the aqueous solution 30～60 minutes, rinse well with secondary water the cooling back; Put into 0.5～2mol/LH then
2SO
4In boiled 30～60 minutes, after rinsing well with secondary water, put into secondary water and soaked 15～20 minutes, be stored at last in the secondary water soak standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100 ℃ through the pretreated proton exchange membrane of (1) step, then at 0.01～0.2mol/L aniline and 0.4～0.6mol/LH
2SO
4Mixed solution in soaked 0.5～1.0 minute; Then proton exchange membrane is put into the electrochemistry of solids pond, with electrochemical method with the polyaniline electro-deposition on the proton exchange membrane surface; The proton exchange membrane that deposition is good is put into 0.4～0.6mol/LH respectively
2SO
4Soaked 15～20 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
The work electrode in electrochemistry of solids pond and electrode is firm system electrode.
The Nafion117 film that proton exchange membrane is produced with DuPont company among the present invention, it is the constant current method that alcohol is used methyl alcohol, electrochemical method, current density range 0.1～0.8mA/cm
2
The preparation-obtained modified proton exchange film capable of reducing alcohol permeation of the inventive method can be used for direct methanol fuel cell.
Compared with the prior art, the present invention has following beneficial effect:
The present invention only uses aniline monomer as raw material, and raw material is simple, is easy to get.The process of handling the Nafion117 film is quite convenient, and simple, need not special installation.Nafion117 film methanol permeability after polyaniline is handled reduces greatly, and proton conductivity only slightly descends.As a comprehensive evaluation index, with respect to the Nafion117 film, the Nafion117 film K/D value increase amplitude of modifying through polyaniline is above two orders of magnitude with proton conductivity and methanol permeability ratio (K/D).
Embodiment
The present invention will be further described below in conjunction with specific embodiment, but the present invention's scope required for protection is not limited to the described scope of embodiment.
Embodiment 1
The preliminary treatment of proton exchange membrane: the H that the Nafion117 film of 2cm * 3cm is put into 3% weight
2O
2Boiled in the aqueous solution 45 minutes, rinse well with secondary water the cooling back; Put into 0.5mol/LH then
2SO
4In boiled 45 minutes, after rinsing well with secondary water, put into secondary water and soaked 15 minutes, be stored at last soak in the secondary water standby;
The methanol permeability D that experiment records the Nafion117 film is 3.952 * 10
-7Cm
2/ s, the proton conductivity K of Modified Membrane is 3.771 * 10
-2/ cm, the K/D value is 9.542 * 10
4
Embodiment 2
The preparation of modified proton exchange film capable of reducing alcohol permeation:
(1) preliminary treatment of proton exchange membrane: the H that the Nafion117 film of 2cm * 3cm is put into 2% weight
2O
2Boiled in the aqueous solution 30 minutes, rinse well with secondary water the cooling back; Put into 0.5mol/LH then
2SO
4In boiled 30 minutes, after rinsing well with secondary water, put into secondary water and soaked 15 minutes, be stored at last soak in the secondary water standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100C through the pretreated proton exchange membrane of (1) step, then at 0.01mol/L aniline and 0.4mol/LH
2SO
4Mixed solution in soaked 0.5 minute; Then proton exchange membrane is put into the electrochemistry of solids pond, with 0.4mA/cm
2Galvanostatic deposition 5 minutes, the deposition electric weight is 0.12C/cm
2The proton exchange membrane that deposition is good is put into 0.4mol/LH
2SO
4Soaked 15 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
The work electrode in electrochemistry of solids pond and electrode is firm system electrode.
The methanol permeability D that experiment records this modified proton exchange film is 2.321 * 10
-8Cm
2/ s, the proton conductivity K of Modified Membrane is 2.550 * 10
-2S/cm, the K/D value is 1.099 * 10
6
Embodiment 3
The preparation of modified proton exchange film capable of reducing alcohol permeation:
(1) preliminary treatment of proton exchange membrane: the H that the Nafion117 film of 2cm * 3cm is put into 5% weight
2O
2Boiled in the aqueous solution 60 minutes, rinse well with secondary water the cooling back; Put into 2mol/LH then
2SO
4In boiled 60 minutes, after rinsing well with secondary water, put into secondary water and soaked 20 minutes, be stored at last soak in the secondary water standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100 ℃ through the pretreated proton exchange membrane of (1) step, then at 0.2mol/L aniline and 0.6mol/LH
2SO
4Mixed solution in soaked 1.0 minutes; Then proton exchange membrane is put into the electrochemistry of solids pond, with 0.4mA/cm
2Galvanostatic deposition 10 minutes, the deposition electric weight is 0.24C/cm
2The proton exchange membrane that deposition is good is put into 0.6mol/LH
2SO
4Soaked 20 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
The work electrode in electrochemistry of solids pond and electrode is firm system electrode.
The methanol permeability D that experiment records this modified proton exchange film is 1.743 * 10
-8Cm
2/ s, the proton conductivity K of Modified Membrane is 2.862 * 10
-2S/cm, the K/D value is 1.642 * 10
6
Embodiment 4
The preparation of modified proton exchange film capable of reducing alcohol permeation:
(1) preliminary treatment of proton exchange membrane: the H that the Nafion117 film of 2cm * 3cm is put into 3% weight
2O
2Boiled in the aqueous solution 45 minutes, rinse well with secondary water the cooling back; Put into 1mol/LH then
2SO
4In boiled 45 minutes, after rinsing well with secondary water, put into secondary water and soaked 15 minutes, be stored at last soak in the secondary water standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100 ℃ through the pretreated proton exchange membrane of (1) step, then at 0.1mol/L aniline and 0.5mol/LH
2SO
4Mixed solution in soaked 0.5 minute; Then proton exchange membrane is put into the electrochemistry of solids pond, with 0.4mA/cm
2Galvanostatic deposition 20 minutes, the deposition electric weight is 0.48C/cm
2The proton exchange membrane that deposition is good is put into 0.5mol/LH
2SO
4Soaked 15 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
The work electrode in electrochemistry of solids pond and electrode is firm system electrode.
The methanol permeability D that experiment records this modified proton exchange film is 4.908 * 10
-8Cm
2/ s, the proton conductivity K of Modified Membrane is 1.983 * 10
-2S/cm, the K/D value is 4.040 * 10
5
Embodiment 5
The preparation of modified proton exchange film capable of reducing alcohol permeation:
(1) preliminary treatment of proton exchange membrane: the H that the Nafion117 film of 2cm * 3cm is put into 3% weight
2O
2Boiled in the aqueous solution 45 minutes, rinse well with secondary water the cooling back; Put into 1mol/LH then
2SO
4In boiled 45 minutes, after rinsing well with secondary water, put into secondary water and soaked 15 minutes, be stored at last soak in the secondary water standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100 ℃ through the pretreated proton exchange membrane of (1) step, then at 0.1mol/L aniline and 0.5mol/LH
2SO
4Mixed solution in soaked 0.5 minute; Then proton exchange membrane is put into the electrochemistry of solids pond, with 0.1mA/cm
2Galvanostatic deposition 40 minutes, the deposition electric weight is 0.24C/cm
2The proton exchange membrane that deposition is good is put into 0.5mol/LH
2SO
4Soaked 15 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
The work electrode in electrochemistry of solids pond and electrode is firm system electrode.
The methanol permeability D that experiment records this modified proton exchange film is 3.209 * 10
-8Cm
2/ s, the proton conductivity K of Modified Membrane is 1.823 * 10
-2S/cm, the K/D value is 5.671 * 10
5
Embodiment 6
The preparation of modified proton exchange film capable of reducing alcohol permeation:
(1) preliminary treatment of proton exchange membrane: the H that the Nafion117 film of 2cm * 3cm is put into 3% weight
2O
2Boiled in the aqueous solution 45 minutes, rinse well with secondary water the cooling back; Put into 1mol/LH then
2SO
4In boiled 45 minutes, after rinsing well with secondary water, put into secondary water and soaked 15 minutes, be stored at last soak in the secondary water standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100 ℃ through the pretreated proton exchange membrane of (1) step, then at 0.1mol/L aniline and 0.5mol/LH
2SO
4Mixed solution in soaked 0.5 minute; Then proton exchange membrane is put into the electrochemistry of solids pond, with 0.2mA/cm
2Galvanostatic deposition 20 minutes, the deposition electric weight is 0.24C/cm
2The proton exchange membrane that deposition is good is put into 0.5mol/LH
2SO
4Soaked 15 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
The work electrode in electrochemistry of solids pond and electrode is firm system electrode.
The methanol permeability D that experiment records this modified proton exchange film is 6.981 * 10
-9Cm
2/ s, the proton conductivity K of Modified Membrane is 2.490 * 10
-2S/cm, the K/D value is 3.567 * 10
6
Embodiment 7
The preparation of modified proton exchange film capable of reducing alcohol permeation:
(1) preliminary treatment of proton exchange membrane: the H that the Nafion117 film of 2cm * 3cm is put into 3% weight
2O
2Boiled in the aqueous solution 45 minutes, rinse well with secondary water the cooling back; Put into 1mol/LH then
2SO
4In boiled 45 minutes, after rinsing well with secondary water, put into secondary water and soaked 15 minutes, be stored at last soak in the secondary water standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100 ℃ through the pretreated proton exchange membrane of (1) step, then at 0.1mol/L aniline and 0.5mol/LH
2SO
4Mixed solution in soaked 0.5 minute; Then proton exchange membrane is put into the electrochemistry of solids pond, with 0.8mA/cm
2Galvanostatic deposition 5 minutes, the deposition electric weight is 0.24C/cm
2The proton exchange membrane that deposition is good is put into 0.5mol/LH
2SO
4Soaked 15 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
The work electrode in electrochemistry of solids pond and electrode is firm system electrode.
The methanol permeability D that experiment records this modified proton exchange film is 1.774 * 10
-8Cm
2/ s, the proton conductivity K of Modified Membrane is 1.639 * 10
-2S/cm, the K/D value is 9.239 * 10
5
Claims (5)
1, the preparation method of modified proton exchange film capable of reducing alcohol permeation is characterized in that comprising the steps:
(1) preliminary treatment of proton exchange membrane: the H that proton exchange membrane is put into 2～5% weight
2O
2Boiled in the aqueous solution 30～60 minutes, rinse well with secondary water the cooling back; Put into 0.5～2mol/LH then
2SO
4In boiled 30～60 minutes, after rinsing well with secondary water, put into secondary water and soaked 15～20 minutes, be stored at last in the secondary water soak standby;
(2) at proton exchange membrane surface deposition polyaniline: will be dried to constant weight at 100 ℃ through the pretreated proton exchange membrane of (1) step, then at 0.01～0.2mol/L aniline and 0.4～0.6mol/LH
2SO
4Mixed solution in soaked 0.5～1.0 minute; Then proton exchange membrane is put into the electrochemistry of solids pond, with electrochemical method with the polyaniline electro-deposition on the proton exchange membrane surface; The proton exchange membrane that deposition is good is put into 0.4～0.6mol/LH respectively
2SO
4Soaked 15～20 minutes in solution and the secondary water, promptly make modified proton exchange film capable of reducing alcohol permeation.
2, the preparation method of modified proton exchange film capable of reducing alcohol permeation according to claim 1 is characterized in that the work electrode in the described electrochemistry of solids of (2) step pond and electrode is firm system electrode.
3, the preparation method of modified proton exchange film capable of reducing alcohol permeation according to claim 1 is characterized in that the described electrochemical method of (2) step is the constant current method, current density range 0.1～0.8mA/cm
2
4, the preparation-obtained modified proton exchange film capable of reducing alcohol permeation of the preparation method of the described modified proton exchange film capable of reducing alcohol permeation of claim 1.
5, the application of the described modified proton exchange film capable of reducing alcohol permeation of claim 3 on direct methanol fuel cell.
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| CN100334750C CN100334750C (en) | 2007-08-29 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102694139A (en) * | 2012-05-18 | 2012-09-26 | 东华大学 | Bacterial cellulose-Nafion sandwich proton exchange membrane and preparation and application thereof |
| CN103123974A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院大连化学物理研究所 | Conducting polymer/metal/proton exchange composite membrane and preparation and application thereof |
| CN110176617A (en) * | 2019-06-05 | 2019-08-27 | 山东大学 | A method of improving NAFION film resistance alcohol selectivity |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7241334B2 (en) * | 2002-05-23 | 2007-07-10 | Columbian Chemicals Company | Sulfonated carbonaceous materials |
| CN1263179C (en) * | 2003-11-18 | 2006-07-05 | 武汉理工大学 | Process for preparing proton composite exchange membrane for high temperature proton exchange membrane fuel battery |
-
2005
- 2005-04-15 CN CNB2005100341327A patent/CN100334750C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103123974A (en) * | 2011-11-18 | 2013-05-29 | 中国科学院大连化学物理研究所 | Conducting polymer/metal/proton exchange composite membrane and preparation and application thereof |
| CN103123974B (en) * | 2011-11-18 | 2014-12-31 | 中国科学院大连化学物理研究所 | Conducting polymer/metal/proton exchange composite membrane and preparation and application thereof |
| CN102694139A (en) * | 2012-05-18 | 2012-09-26 | 东华大学 | Bacterial cellulose-Nafion sandwich proton exchange membrane and preparation and application thereof |
| CN102694139B (en) * | 2012-05-18 | 2015-08-12 | 东华大学 | The sandwich proton exchange membrane of bacteria cellulose-Nafion and Synthesis and applications |
| CN110176617A (en) * | 2019-06-05 | 2019-08-27 | 山东大学 | A method of improving NAFION film resistance alcohol selectivity |
| CN110176617B (en) * | 2019-06-05 | 2021-03-30 | 山东大学 | Method for improving alcohol resistance selectivity of NAFION membrane |
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Granted publication date: 20070829 Termination date: 20120415 |