CN100374492C - Method for preparing chitose proton exchange membrance for fuel cell - Google Patents
Method for preparing chitose proton exchange membrance for fuel cell Download PDFInfo
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- CN100374492C CN100374492C CNB2005101302372A CN200510130237A CN100374492C CN 100374492 C CN100374492 C CN 100374492C CN B2005101302372 A CNB2005101302372 A CN B2005101302372A CN 200510130237 A CN200510130237 A CN 200510130237A CN 100374492 C CN100374492 C CN 100374492C
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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
- 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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- 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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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The present invention discloses a method for preparing chitosan proton exchanging membranes for fuel batteries. After chitosan powder with the grain diameter of 40 to 100 is added into acetic acid solution with the concentration of 0.083 to 0.83 mol/L and is sufficiently and uniformly stirred, a membrane is paved on a quartz glass plate by using the technology of flow extending membrane manufacture, the quartz glass plate is placed into a baking oven with the temperature of 45 DEG C to 70 DEG C to be dried and is taken out after 2 to 8 hours, the quartz glass plate is placed into sodium hydroxide solution with the concentration of 0.5 to 4 mol/L to be dipped to remove the membrane, and then the membrane is placed into sulfuric acid solution with the concentration of 0.1 to 1 mol/L to carry out cross connection and is taken out after 8 to 15 hours. After the membrane is washed by ion removing water, a chitosan proton exchanging membrane for fuel batteries is obtained and has the proton conducting rate of 0.16% to 6% under the temperature of 10 DEG C to 80 DEG C.
Description
Technical field
The present invention relates to the act as a fuel preparation method and the chitosan proton exchange membrane thereof of proton exchange membrane of battery of a kind of derivative that adopts the chitin (biological raw material) that nature exists.
Background technology
Fuel cell is the chemical reaction by means of fuel in the battery, and chemical energy is converted into a kind of energy device of electric energy, is a kind of novel efficient chemical power source.Because fuel cell in reaction process, does not produce any deleterious refuse, and the transformation efficiency height, so be subjected to people's common concern.
Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, PEMFC) be a class with proton exchange membrane as electrolytical fuel cell system, this fuel cell also often be called as solid polymer fuel cells (polymer electrolyte fuel cell, PEFC).Membrane electrode is the core of Proton Exchange Membrane Fuel Cells, and it is made up of proton exchange membrane, the catalyzer that is coated in the proton exchange membrane both sides and gas diffusion layers.Proton exchange membrane is as the important carrier of proton conduction in the membrane electrode, and it has superior thermostability and proton conductive, but its production process complexity costs an arm and a leg, and selects perviousness relatively poor, need utilize water to come proton conducting as medium.
Chitin (1,4-2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-callose is abbreviated as CTS) is that present occurring in nature is only second to cellulosic second largest class biomaterial, also is the outer maximum nitrogenous natural organic matter of quantity of isolating protein on the earth.Chitosan (1; 4-2-amino-2-deoxidation-callose; be abbreviated as CS) as the product of chitin deacetylase base; numerous hydroxyls and amino are arranged on the molecular chain; be easy to carry out chemical modification and crosslinked action; have characteristics such as good film-forming properties, heat retaining property, in food, chemical industry, medicine and other fields extensive application.
Summary of the invention
The objective of the invention is to propose a kind of biological raw material preparation method of battery that act as a fuel that adopt with the chitosan film of proton exchange membrane, to adopt casting film technology system chitosan film behind the chitosan powder adding acetic acid, it is crosslinked then chitosan film to be put into sulfuric acid, makes and forms the proton conduction passage between amino in the chitosan and the sulfate ion.Chitosan proton exchange membrane complete processing of the present invention is simple, low production cost, and material source is extensive, does not cause second environmental pollution.
The present invention is a kind of preparation method of chitose proton exchange membrance for fuel cell, has the following steps:
The first step at normal temperatures and pressures, adds particle diameter 40～100 purpose chitosan powder fully to stir in the acetum that concentration is 0.083～0.83mol/L and makes chitosan-acetic acid solution, and described chitosan dosage is that the described acetum of every 500ml needs 5～20g;
Second step, adopt casting film technology that described chitosan-acetic acid solution is sprawled on quartz glass plate, in 45 ℃～70 ℃ baking oven, take out behind dry 2～8h, the sodium hydroxide solution of putting into concentration again and be 0.5～4mol/L is dipped to chitosan film and comes off from quartz glass plate, takes out chitosan film and rinses out its surperficial sodium hydroxide solution with deionized water;
In the 3rd step, it is to take out behind the crosslinked 8～15h of 0.1～1mol/L sulphuric acid soln that the chitosan film after cleaning is put into concentration, promptly obtains chitose proton exchange membrance for fuel cell with after the washed with de-ionized water 1～5 time.
In the preparation method of described chitosan proton exchange membrane, its chitosan powder is that molecular weight is 5～70,000, and deacetylation is 70～90% food grade chitosan.
In the preparation method of described chitosan proton exchange membrane, the chitosan film thickness of its curtain coating on quartz glass plate is 30～60 μ m.
The advantage of proton exchange membrane preparation method of the present invention is: (1) chitosan is the product of the solid waste chitin of aquatic products industry generations such as shrimp shell, crab shell through deacetylation, with its proton exchange membrane of manufacturing fuel cell is to economize on resources, turn waste into wealth, the means that make full use of the natural resources also make the raw materials cost of fuel cell be minimized simultaneously; (2) preparation technology as proton exchange membrane is simple, easily realizes the industrialization batch process; (3) in the chitosan proton exchange membrane preparation process, do not produce deleterious material, environment is not polluted.
Description of drawings
Fig. 1 is the proton conductivity graphic representation of proton exchange membrane under 10 ℃～80 ℃ conditions that contains 2.5% chitosan.
Fig. 2 is that chitosan film carries out crosslinked chemical reaction flow process.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Employed chitosan derives from the chitin in shrimp shell or the crab shell among the present invention, then chitin is handled and is obtained through deacetylation.Chitosan has good film-forming properties, does not relate to toxicant in film-forming process, and membrane equipment and technology are easy.This film tensile strength is big, good toughness, alkaline-resisting and organic solvent-resistant.Acidproof after crosslinked, thermotolerance is better than cellulose acetate membrane, and is nontoxic simultaneously, wetting ability big, biomass cells is had fabulous consistency.
The present invention is a kind of preparation method of chitose proton exchange membrance for fuel cell, it has the following steps: the first step, at normal temperatures and pressures, the chitosan powder added fully to stir in the acetum that concentration is 0.083～0.83mol/L make chitosan-acetic acid solution, described chitosan dosage is that the described acetum of every 500ml needs 5～20g;
Second step, adopt casting film technology that described chitosan-acetic acid solution is sprawled on quartz glass plate, in 45 ℃～70 ℃ baking oven, take out behind dry 2～8h, the sodium hydroxide solution of putting into concentration again and be 0.5～4mol/L is dipped to chitosan film and comes off from quartz glass plate, takes out chitosan film and rinses out its surperficial sodium hydroxide solution with deionized water;
In the 3rd step, it is to take out behind the crosslinked 8～15h of 0.1～1mol/L sulphuric acid soln that the chitosan film after cleaning is put into concentration, promptly obtains chitose proton exchange membrance for fuel cell with after the washed with de-ionized water 1～5 time.
It is 0.16 * 10 that 5210 lock-in amplifiers that adopt 273A constant potential/galvanostat that U.S. Princeton Applied Research company produces and PerkinElmer company to produce the above-mentioned chitosan proton exchange membrane for preparing are tested its proton conductivity at 10 ℃～80 ℃
-2～6.00 * 10
-2, range of frequency: 0.1～1 * 10
5Hz, the current/voltage amplitude is: ± 5mV.
In the present invention, the chitosan proton exchange membrane for preparing should be kept in the deionized water of normal temperature, is in order to prevent that chitosan proton exchange membrane from becoming dry, to guarantee in the chitosan film higher water ratio being arranged.
The thickness of the chitosan film of the present invention preparation is 30～60 μ m, and the thickness of film is that the intensity of thick film is better as an important technical parameter of proton exchange membrane in the fuel cell, but membrane resistance also the phase strain is big.In theory, reduce the thickness of film, help reducing the resistance of film, improve the electric conductivity of film and the operating voltage and the energy density of battery.But the thickness of film is crossed the young pathbreaker and is caused that the seepage of anode fuel and the mechanical property of film descend, and shorten the working life of film.Another advantage that reduces film thickness is to make the contained bigger concentration gradient of water formation in water that negative electrode generates and the anode side form, the water anode that helps cathodic reaction to generate moves, proton exchange membrane water content in the course of the work is provided, solves the dry problem of film.The chitosan proton exchange membrane thickness of the present invention's development depends primarily on the quantity that adopts casting film technology to spread over the solution on the quartz glass plate.
The proton exchange membrane that general fuel cell is used can cause area to change and distortion through swelling, thereby influences the use properties of film.The chemical stability of what and material of the active group in the mould material all will have influence on degree of swelling, material aging for example, and the macromolecular chain fracture can make the swelling capacity of film become big.The chitose crosslinked membrane swelling capacity that the present invention makes is 2.0% only, make membrane electrode after, under full wet condition, volume does not have obvious variation, can the size and the performance of membrane electrode not exerted an influence.
Higher water ratio has very big influence to the proton conductivity of chitosan proton exchange membrane, because the content of water is that the polymkeric substance internal penetration is pressed the equilibrated result in the film, thereby the crosslinked and exchange capacity of superpolymer all can have influence on the water ratio of film in the film, water ratio not only influences proton conduction, and influences the dissolving diffusion of oxygen in film.Battery in order to obtain maximum proton conductivity, requires water content moderate in operational process.
Loading capacity (IEC) has reflected that chitosan proton exchange membrane carries out a kind of ability of ion conversion.The film that exchange capacity is big conducts electricity very well, but because the wetting ability of active group makes the also corresponding raising of water ratio of film, film is soft, and the aperture is big, and the selectivity of film is relatively poor.For perfluorinated sulfonic acid ion exchange resin, the IEC value is big more, the expression copolymer resin in contained perfluoroalkyl vinyl ether chain link the more, under other condition same cases, the resistance of film is lower, can obtain higher battery performance.
Embodiment 1:System contains the chitosan proton exchange membrane of 2.5% chitosan
At normal temperatures and pressures, with particle diameter 80 order molecular weight is 60,000, deacetylation is that to put into concentration be that 1% 500ml acetic acid fully stirs into chitosan-acetic acid solution for 75% 12.5g food grade chitosan powder, chitosan-acetic acid solution being adopted casting film legal system thickness is the film of 40 μ m again, makes chitosan proton exchange membrane behind the dry 6h then in 60 ℃ baking oven; The sodium hydroxide solution of then chitosan film being put into concentration and be 2mol/L is dipped to film wash-out from the sheet glass, takes out the back with washed with de-ionized water 3 times, the sodium hydroxide solution on chitosan film surface is cleaned got final product; It is to take out behind the crosslinked 12h of 0.5mol/L sulphuric acid soln that chitosan film after will cleaning is again put into concentration, uses washed with de-ionized water 2 times, promptly gets chitose proton exchange membrance for fuel cell.
Cut 2cm * 4cm chitosan proton exchange membrane, adopt the whole impedance test, range of frequency 0.1～1 * 10
5Hz, the current/voltage amplitude is ± 5mV, is 1.50 * 10 at 10 ℃ proton conductivities
-2, be 1.53 * 10 at 20 ℃ proton conductivities
-2, be 2.52 * 10 at 40 ℃ proton conductivities
-2, be 3.92 * 10 at 60 ℃ proton conductivities
-2, be 6.00 * 10 at 80 ℃ proton conductivities
-2, contain 2.5% chitosan proton exchange membrane the proton conduction rate curve as shown in Figure 1.
See also shown in Figure 2ly, the present invention adopts sulfuric acid H in crosslinked preparation process
2SO
4As linking agent, through the crosslinked chitosan of persulfuric acid, its proton conduction becomes strides the interchain conduction.As can be seen, this interchain sulfate ion is the proton conduction passage, and along with the increase and the test temperature increase of chitosan concentration, proton conductivity all increases.Its former because: along with the increase of chitosan concentration, the corresponding increase of the sulfuric acid molecule that engages, thereby improved the conductivity of proton; And the proton conductivity of sulfate ion has been accelerated in the increase of temperature.
Embodiment 2:System contains the chitosan proton exchange membrane of 1% chitosan
At normal temperatures and pressures, with particle diameter 80 order molecular weight is 60,000, deacetylation is that to put into concentration be that 1% 500ml acetic acid fully stirs into chitosan-acetic acid solution for 75% 5g food grade chitosan powder, chitosan-acetic acid solution being adopted casting film legal system thickness is the film of 30 μ m again, makes chitosan proton exchange membrane behind the dry 6h then in 60 ℃ baking oven; The sodium hydroxide solution of then chitosan film being put into concentration and be 2mol/L is dipped to film wash-out from the sheet glass, takes out the back with washed with de-ionized water 3 times, the sodium hydroxide solution on chitosan film surface is cleaned got final product; It is to take out behind the crosslinked 12h of 0.5mol/L sulphuric acid soln that chitosan film after will cleaning is again put into concentration, uses washed with de-ionized water 2 times, promptly gets chitose proton exchange membrance for fuel cell.
It is as shown in table 1 to cut that 2cm * the 4cm chitosan proton exchange membrane is measured its performance:
Table 1 contains the performance perameter of the chitosan proton exchange membrane of 1% chitosan
| Thickness (μ m) | Swelling capacity (%) | Water ratio (%) | Loading | Proton conductivity | 10 -2 | ||||
| 10 |
40 |
60 |
|||||||
| 30 | 2.0％ | 129％ | 1.28 | 0.11×10 -2 | 0.23×10 -2 | 0.26×10 -2 | |||
Claims (1)
1. the preparation method of a chitose proton exchange membrance for fuel cell is characterized in that having the following steps:
The first step at normal temperatures and pressures, adds particle diameter 40～100 purpose chitosan powder fully to stir in the acetum that concentration is 0.083～0.83mol/L and makes chitosan-acetic acid solution, and described chitosan dosage is that the described acetum of every 500ml needs 5～20g;
Described chitosan powder is that molecular weight is 5～70,000, and deacetylation is 70～90% food grade chitosan;
Second step, adopt casting film technology that described chitosan-acetic acid solution is sprawled on quartz glass plate, in 45 ℃～70 ℃ baking oven, take out behind dry 2～8h, the sodium hydroxide solution of putting into concentration again and be 0.5～4mol/L is dipped to chitosan film and comes off from quartz glass plate, takes out chitosan film and rinses out its surperficial sodium hydroxide solution with deionized water;
The chitosan film thickness of curtain coating on quartz glass plate is 30～60 μ m;
In the 3rd step, it is to take out behind the crosslinked 8～15h of 0.1～1mol/L sulphuric acid soln that the chitosan film after cleaning is put into concentration, promptly obtains chitose proton exchange membrance for fuel cell with after the washed with de-ionized water 1～5 time.
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| CN100374492C true CN100374492C (en) | 2008-03-12 |
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| CN101240077B (en) * | 2007-12-19 | 2011-07-27 | 天津大学 | Chitosan and acroleic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer mixing film, preparation method and application thereof |
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| CN108232255A (en) * | 2016-12-19 | 2018-06-29 | 天津艾博胜环保科技有限公司 | The preparation method of Metal semi-fuel cells chitosan film electrode |
| CN107093760A (en) * | 2017-05-05 | 2017-08-25 | 湖北工程学院 | The preparation method of Kynoar loading chitosan PEM |
| CN108155406B (en) * | 2017-12-26 | 2021-04-06 | 中国科学院青岛生物能源与过程研究所 | Phosphosilicate glass doped chitosan intermediate-temperature proton exchange membrane and preparation method thereof |
| CN108659144A (en) * | 2018-05-31 | 2018-10-16 | 华南理工大学 | A kind of chitosan-based ion conductive material of purine-containing structure and preparation method thereof |
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| US5093319A (en) * | 1989-10-31 | 1992-03-03 | Pfizer Hospital Products Group, Inc. | Use of derivatives of chitin soluble in aqueous solutions for preventing adhesions |
| CN1119553A (en) * | 1994-09-28 | 1996-04-03 | 中国人民解放军军事医学科学院卫生装备研究所 | Preparation of chitosan charged microporous filtering film by dip-coating method |
| CN1375350A (en) * | 2002-01-04 | 2002-10-23 | 上海师范大学 | Prepn. of reverse osmose membrane for N-acetyl chitosan |
| CN1445263A (en) * | 2002-03-15 | 2003-10-01 | 宋海涛 | Method for preparing chitosan film not dissolved in acids, alkalis and water |
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2005
- 2005-12-15 CN CNB2005101302372A patent/CN100374492C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5093319A (en) * | 1989-10-31 | 1992-03-03 | Pfizer Hospital Products Group, Inc. | Use of derivatives of chitin soluble in aqueous solutions for preventing adhesions |
| CN1119553A (en) * | 1994-09-28 | 1996-04-03 | 中国人民解放军军事医学科学院卫生装备研究所 | Preparation of chitosan charged microporous filtering film by dip-coating method |
| CN1375350A (en) * | 2002-01-04 | 2002-10-23 | 上海师范大学 | Prepn. of reverse osmose membrane for N-acetyl chitosan |
| CN1445263A (en) * | 2002-03-15 | 2003-10-01 | 宋海涛 | Method for preparing chitosan film not dissolved in acids, alkalis and water |
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