CN100434478C - Medium temperature proton conductive mateiral basedon hydrophilic carbon nano tube and its preparing method - Google Patents
Medium temperature proton conductive mateiral basedon hydrophilic carbon nano tube and its preparing method Download PDFInfo
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- CN100434478C CN100434478C CNB2006101166480A CN200610116648A CN100434478C CN 100434478 C CN100434478 C CN 100434478C CN B2006101166480 A CNB2006101166480 A CN B2006101166480A CN 200610116648 A CN200610116648 A CN 200610116648A CN 100434478 C CN100434478 C CN 100434478C
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Abstract
The present invention belongs to the field of functional polymer material and electrochemical technology, and is especially one kind of medium temperature protonic conducting material based on hydrophilic carbon nanotube and sulfonic group-containing polymer and its preparation process. The present invention features that sulfonic group-containing polymer and hydrophilic carbon nanotube are combined to obtain protonic conducting film material with water keeping capacity raised both chemically and structurally. The prepared protonic conducting film material has high protonic conducting performance even in the temperature over the boiling point of water, and may be used in proton exchanging film and film electrode in medium temperature fuel cell.
Description
Technical field
The invention belongs to macromolecular material and technical field of electrochemistry, be specifically related under a kind of middle temperature environment that can be used for more than 100 ℃ based on composite proton electro-conductive material of sulfonated polymer and hydrophilic carbon nano tube and preparation method thereof.
Background technology
In temperature (100-200 ℃) polymer dielectric film fuel cell (PEMFC) compare with normal temperature PEMFC at present commonly used and have the following advantages: (1) eelctro-catalyst active and to the permissible concentration height of impurity such as CO; (2) might significantly reduce the consumption of noble metal electrocatalysts such as Pt; (3) the electrode kinetics characteristic improves, fuel availability and energy capacity of battery density height; (4) saved the humidification system of battery; (5) simplified the cooling system of battery.But middle temperature PEMFC also has higher requirement to materials such as ionogen, require proton exchange membrane (PEM) under 100-200 ℃ working temperature, to still have enough proton conductives and transport capacity, and this is a difficult problem for perfluorinated sulfonic acid hydration shells such as Nafion, because water is in evaporation easily more than 100 ℃, its proton conductive performance is sharply reduced, and PEMFC commonly used in fact at present make degradation of cell performance will dewatering more than 70 ℃.Adopt hydrophilic hollow Nano microsphere and aquation sulfonate film compound, can improve wherein warm water retention capacity (letter spit of fland, Pu, wangdan, Yang Zhenglong, Chinese invention patent, application number 200510112402.1).
The present invention is by introducing hydrophilic carbon nanotube in containing the polymkeric substance of sulfonic acid group, form and space structure two aspects improve the water retention capacity of system simultaneously from chemical ingredients.Prepared proton-conducting membrane material still has proton conductive performance preferably more than the boiling point of water, can be used for the proton exchange membrane and the membrane electrode of intermediate temperature fuel cell.The similar approach report is not arranged in the document as yet.
Summary of the invention
The object of the present invention is to provide warm proton-conducting membrane material and preparation method thereof in a kind of new polymers that is suitable for electrochemical devices such as middle temperature (100-200 ℃) fuel cell.
The proton-conducting membrane material that can under 100 ℃-200 ℃ middle temperature environment, work that the present invention proposes, by the compound system that modified carbon nano-tube aqueous dispersions and sulfonated polymer are formed, the proportioning that each components in mass portion is counted meter is as follows:
Sulfonated polymer 1,
Hydrophilic carbon nano tube 0.00007-0.001.
Described sulfonated polymer, its main chain or side chain contain sulfonic acid group, have the proton conductive ability under room temperature and hydrated state.Have just like sulfonated polyphenyl and imidazoles (sPBI), sulfonated polyimide (sPI) or polyfluoro sulfonate film (as Nafion (anti-fluorine)) etc., but be not limited only to this.
Described hydrophilic carbon nano tube is obtained hydrophilic radicals such as surperficial hydroxyl, carboxyl after hydrophilically modified by single wall or multi-walled carbon nano-tubes.
Described carbon nano-tube modification process such as following:
Is 2.8-3.3 with carbon nanotube in volume ratio: supersound process 25-35min in the vitriol oil/concentrated nitric acid of 1 at 100-110 ℃ of reflux condensation mode 4-6h, is the cellulose membrane vacuum filtration of 0.22 μ m with the aperture, and deionized water is washed till neutrality; The carbon nanotube of learning from else's experience and handling adds water, is made into aqueous dispersions.Promptly get nitration mixture oxide/carbon nanometer tube aqueous dispersions.
Also can further handle this dispersion liquid:
Get the carbon nanotube 25-30mg that above-mentioned nitration mixture oxide treatment is crossed, be dispersed in the DMF (N of 50ml, dinethylformamide) in, supersound process 25-35min, the Diisopropyl azodicarboxylate that adds 2-20g band cyano group, room temperature is led to nitrogen deoxygenation 25-35min, and 65-70 ℃ of magnetic agitation 110-130min is cooled to room temperature.With the aperture is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m, DMF washing 3～5 times.The carbon nanotube of above-mentioned Diisopropyl azodicarboxylate modification is dispersed in the aqueous sodium hydroxide solution of 50ml 2mol/L, make cyan-hydrolysis become carboxyl at 65-70 ℃ of reflux condensation mode 80-100min., be cooled to room temperature, with the aperture is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m, deionized water wash 3～5 times.To add water through the carbon nanotube of above-mentioned processing, be made into aqueous dispersions.Promptly get surperficial carboxylated carbon nanotube aqueous dispersions.
The preparation method of described a kind of middle temperature proton conducting material based on hydrophilic carbon nano tube, its concrete steps are as follows: with hydrophilic carbon nano tube ultra-sonic dispersion 12-20min in solvent, sulfonated polymer is dissolved, be made into the solution of 0.1-10% concentration, mass ratio according to sulfonated polymer and hydrophilic carbon nano tube 1: 0.00007-0.001, the dispersion liquid that adds hydrophilic carbon nano tube, ultra-sonic dispersion is even, cast on the polyfluortetraethylene plate, remove most of solvent under the infrared lamp, 65-75 ℃ of baking 12-24h promptly gets the composite proton conducting film that contains hydrophilic carbon nano tube in vacuum drying oven.
The present invention adopts hydrophilic carbon nano tube, its both ends open, and hydrophilic radicals such as surperficial hydroxyl, carboxyl have good water retention capacity, can delay the evaporation of water under middle high temperature, thereby obtain good proton conductive performance under comparatively high temps.With Nafion 112/ hydrophilic carbon nano tube composite membrane is example, and its proton conductive performance still can reach 10 under 110 ℃
-3, and Nafion 112 has reduced to 10 90 ℃ of following proton conductive abilities
-5Thereby proved that it has good middle temperature water retention capacity.Simultaneously the water ratio of composite membrane is varied with temperature curve and tests, find its at normal temperatures water ratio obviously improve, and dehydration under comparatively high temps has confirmed that further composite membrane has good middle temperature water retention capacity.Composite membrane is carried out infrared test, find that hydrophilic carbon nano tube and polymeric matrix have good consistency.
Description of drawings
The infrared figure of Fig. 1 Nafion 112/ hydrophilic carbon nano tube composite membrane.
The proton conductivity of Fig. 2 Nafion 112/ hydrophilic carbon nano tube composite membrane varies with temperature figure.
Embodiment
Following examples are only for further specifying the present invention, are not violating under the purport of the present invention, and the present invention should be not limited to the content that following experimental example is specifically expressed.
Used starting material are as follows:
Carbon nanotube (caliber 10nm～20nm, length 50 μ m, purity＞95wt%, the organic institute in Chinese Academy of Sciences Chengdu) Nafion 112 resins, DuPont company product
SPBI is according to document (Appleby A., J Fuel Cell System[M], New York, Plenum Press, 1993.) prepared in laboratory.
Embodiment 1
The preparation of nitration mixture oxide/carbon nanometer tube aqueous dispersions: is supersound process 30min in the vitriol oil/concentrated nitric acid of 3: 1 with carbon nanotube in volume ratio, at 100 ℃ of reflux condensation mode 4h, with the aperture is the cellulose membrane vacuum filtration of 0.22 μ m, deionized water is washed till neutrality, scrape to a bottle with the ox horn spoon, add water, be made into aqueous dispersions.Get a clean sheet glass, W weighs
1, drip the carbon nanotube aqueous dispersions of 1ml thereon, oven dry, W weighs
2, (W
2-W
1)/1 promptly gets the concentration (g/ml) of carbon nanotube aqueous dispersions.
The preparation of Nafion 112 solution: Nafion 112 resins are dissolved in N, in the dinethylformamide, under 180 ℃ and nitrogen protection, dissolve 1h, it is fully dissolved, make 5% solution.
The preparation of composite membrane:
Raw materials used proportioning is as follows:
5 parts of nitration mixture oxide/carbon nanometer tubes (mass fraction)
112 10000 parts of Nafion (mass fraction)
With nitration mixture oxide/carbon nanometer tube aqueous dispersions supersound process 15min., according to nitration mixture oxide/carbon nanometer tube: Nafion 112 is that 5: 10000 mass ratio prepares mixing solutions, stir, be poured on the polyfluortetraethylene plate, remove most of solvent under the infrared lamp, tweezers peel, and 70 ℃ of bakings of vacuum drying oven 12h just gets composite membrane.
The infrared test of composite membrane: polymeric film vacuum-drying to constant weight, is measured its infrared spectra with Fourier transformation infrared spectrometer Magna-550, and the result as shown in Figure 1
The mensuration of composite membrane proton conductive performance: composite membrane is steeped 24h in 15% sulfuric acid, again at deionization bubbly water 24h.With alternating current impedance instrument (EG ﹠amp with 273 type potentiostat/galvanostats and 5210 type lock-in amplifiers; G PrincetonApplied Research Co.) composite impedance of mensuration composite membrane changes into the direct current proton conductivity by calculating again.The proton conductive performance of composite membrane as shown in Figure 2.
Embodiment 2
The preparation of nitration mixture oxide/carbon nanometer tube aqueous dispersions: is supersound process 35min in the vitriol oil/concentrated nitric acid of 3.2: 1 with carbon nanotube in volume ratio, at 110 ℃ of reflux condensation mode 6h, with the aperture is the cellulose membrane vacuum filtration of 0.22 μ m, deionized water is washed till neutrality, scrape to a bottle with the ox horn spoon, add water, be made into aqueous dispersions.Get a clean sheet glass, W weighs
1, drip the carbon nanotube aqueous dispersions of 1ml thereon, oven dry, W weighs
2, (W
2-W
1)/1 promptly gets the concentration (g/ml) of carbon nanotube aqueous dispersions.
The preparation of sPBI solution: sPBI is dissolved in a certain amount of 1-Methyl-2-Pyrrolidone, dissolves 2h down, it is fully dissolved at 60 ℃.
The preparation of composite membrane:
Raw materials used proportioning is as follows:
7 parts of nitration mixture oxide/carbon nanometer tubes (mass fraction)
10000 parts of sPBI (mass fraction)
With nitration mixture oxide/carbon nanometer tube aqueous dispersions supersound process 20min, be that 7: 10000 mass ratio prepares mixing solutions according to carbon nanotube: sPBI, stir, be poured on the polyfluortetraethylene plate, remove most of solvent under the infrared lamp, tweezers peel, 70 ℃ of bakings of vacuum drying oven 24h just gets composite membrane.
Its infrared test, proton conductivity test, water cut test and example 1 are described similar.Its proton conductivity is similar as shown in Figure 2 with the variation of temperature curve.
Embodiment 3
The preparation of surface carboxylic carbon nano-tube aqueous dispersions: is supersound process 30 minutes in the vitriol oil/concentrated nitric acid of 3: 1 with carbon nanotube in volume ratio, at 100 ℃ of reflux condensation mode 4h, with the aperture is the cellulose membrane vacuum filtration of 0.22 μ m, deionized water is washed till neutrality, scrape to a bottle with the ox horn spoon, add water, be made into aqueous dispersions.
Get a clean sheet glass, W weighs
1, drip the carbon nanotube aqueous dispersions of 1ml thereon, oven dry, W weighs
2, (W
2-W
1)/1 promptly gets the concentration (g/ml) of carbon nanotube aqueous dispersions.
Get the carbon nanotube 30mg that above-mentioned nitration mixture oxide treatment is crossed, be dispersed among the DMF (N, dinethylformamide) of 50ml, supersound process 30min. adds the 2g Diisopropyl azodicarboxylate, the logical nitrogen deoxygenation of room temperature 25 minutes, and 70 ℃ of magnetic agitation 120min. are cooled to room temperature.With the aperture is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m, DMF washing 3～5 times.
The carbon nanotube of above-mentioned Diisopropyl azodicarboxylate modification being dispersed in the sodium hydroxide of 50ml 2mol/L, at 70 ℃ of reflux condensation mode 90min., being cooled to room temperature, is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m with the aperture, deionized water wash 3～5 times.Scrape to a bottle with the ox horn spoon, add water, be made into aqueous dispersions.
The preparation of sPBI solution: sPBI is dissolved in a certain amount of 1-Methyl-2-Pyrrolidone, dissolves 2h down, it is fully dissolved at 60 ℃.
The preparation of composite membrane:
Raw materials used proportioning is as follows
Surface 5 parts of carboxylic carbon nano-tubes (mass fraction)
10000 parts of sPBI (mass fraction)
With the ultrasonic 15min. of carbon nanotube aqueous dispersions, be that 5: 10000 mass ratio prepares mixing solutions according to surperficial carboxylic carbon nano-tube: sPBI, stir, be poured on the polyfluortetraethylene plate, remove most of solvent under the infrared lamp, tweezers peel, 65 ℃ of bakings of vacuum drying oven 24h just gets composite membrane.
The infrared test of composite membrane, proton conductive performance are tested, water cut test is similar to Example 1, and it is similar as shown in Figure 2 that its proton conductivity varies with temperature curve.
Embodiment 4
The preparation method of surface carboxylic carbon nano-tube aqueous dispersions: is supersound process 30min. in the vitriol oil/concentrated nitric acid of 2.8: 1 with carbon nanotube in volume ratio, at 100 ℃ of reflux condensation mode 4h, with the aperture is the cellulose membrane vacuum filtration of 0.22 μ m, deionized water is washed till neutrality, scrape to a bottle with the ox horn spoon, add water, be made into aqueous dispersions.Get the carbon nanotube 30mg that above-mentioned nitration mixture oxide treatment is crossed, be dispersed among the DMF (N, dinethylformamide) of 50ml, supersound process 30min., the Diisopropyl azodicarboxylate of adding 2g cyano-containing, room temperature is led to nitrogen deoxygenation 25min., 70 ℃ of magnetic agitation 120min. are cooled to room temperature.With the aperture is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m, DMF washing 3～5 times.The carbon nanotube of above-mentioned Diisopropyl azodicarboxylate modification is dispersed in the aqueous sodium hydroxide solution of 50ml 2mol/L, make cyan-hydrolysis become carboxyl at 70 ℃ of reflux condensation mode 90min., being cooled to room temperature, is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m with the aperture, deionized water wash 3～5 times.Scrape to a bottle with the ox horn spoon, add water, be made into aqueous dispersions.
The preparation of Nafion 112 solution: the Nafion112 resin is dissolved in N, in the dinethylformamide, under 180 ℃ and nitrogen protection, dissolves 1h, it is fully dissolved, make 5% solution.
The preparation of composite membrane:
Raw materials used proportioning is as follows
Surface 10 parts of carboxylic carbon nano-tubes (mass fraction)
112 10000 parts of Nafion (mass fraction)
With the ultrasonic 15min. of surperficial carboxylic carbon nano-tube aqueous dispersions, according to surperficial carboxylic carbon nano-tube: Nafion 112 is that 10: 10000 mass ratio prepares mixing solutions, stir, cast on the tetrafluoroethylene template, remove most of solvent under the infrared lamp, tweezers peel, and 70 ℃ of baking 24h just get composite membrane in the vacuum drying oven.
Its infrared test, proton conductive performance, water cut test are similar to Example 1.The proton conductivity of composite membrane is similar as shown in Figure 2 with the variation of temperature curve.
In the foregoing description, the parameter of each component raw material and consumption and preparation process only is the representative of choosing in order to describe invention.In fact a large amount of experiments show, in summary of the invention part institute restricted portion, all can obtain the similar proton exchange membrane of the foregoing description.
Claims (4)
1. middle temperature proton conducting material based on hydrophilic carbon nano tube is characterised in that by sulfonated polymer and hydrophilic carbon nano tube suspension blend to prepare that its one-tenth is grouped into the quality share and is expressed as:
Sulfonated polymer 1,
Hydrophilic carbon nano tube 0.00007-0.001,
Wherein, described sulfonated polymer is sulfonated polyphenyl and imidazoles or polyfluoro sulfonate film; The main chain or the side chain of its polymkeric substance contain sulfonic acid group, have the proton conductive ability under normal temperature and hydrated state;
Described hydrophilic carbon nano tube is obtained after hydrophilically modified by single wall or multi-walled carbon nano-tubes, its surperficial hydroxyl and/or carboxylated hydrophilic group.
2, a kind of preparation method of the middle temperature proton conducting material based on hydrophilic carbon nano tube as claimed in claim 1, its concrete steps are as follows:
With hydrophilic carbon nano tube in solvent ultra-sonic dispersion 12-20 minute; Sulfonated polymer is dissolved, be made into the solution that concentration is 0.1-10%, mass ratio according to sulfonated polymer and hydrophilic carbon nano tube 1: 0.00007-0.001, the dispersion liquid that adds hydrophilic carbon nano tube, ultra-sonic dispersion is even, casts on the polyfluortetraethylene plate, removes most of solvent under the infrared lamp, vacuum drying oven 65-75 ℃ of baking 12-24 hour, promptly get the composite proton conducting film that contains hydrophilic carbon nano tube.
3. preparation method according to claim 2 is characterized in that the preparation process of described hydrophilic carbon nano tube is as follows:
Is 2.8-3.3 with carbon nanotube in volume ratio: in the vitriol oil/concentrated nitric acid of 1 supersound process 25-35 minute, at 100-110 ℃ of reflux condensation mode 4-6h, with the aperture is the cellulose membrane vacuum filtration of 0.22 μ m, deionized water is washed till neutrality, get treated carbon nanotube, add water, be made into aqueous dispersions, promptly get the carbon nanotube aqueous dispersions of nitration mixture oxidation modification.
4, preparation method according to claim 3, it is characterized in that further getting the carbon nanotube 25-30mg that described nitration mixture oxide treatment is crossed, be dispersed in the N of 50ml, in the dinethylformamide, supersound process 25-35 minute, add the Diisopropyl azodicarboxylate that 2-20g is with cyano group, the logical nitrogen deoxygenation of room temperature 25-35 minute, 70 ℃ magnetic agitation 110-130 minute, be cooled to room temperature; With the aperture is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m, duplicates washing 3～5 times; Above-mentioned carbon nanotube through the Diisopropyl azodicarboxylate modification is dispersed in the aqueous sodium hydroxide solution of 50ml 2mol/L, at 65-70 ℃ of reflux condensation mode 80-100 minute, make cyan-hydrolysis become carboxyl, be cooled to room temperature, with the aperture is the polyvinylidene fluoride film vacuum filtration of 0.22 μ m, deionized water wash 3～5 times; To add entry through the carbon nanotube of above-mentioned processing, be made into aqueous dispersions, promptly get surperficial carboxylated carbon nanotube aqueous dispersions.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010150189A1 (en) * | 2009-06-23 | 2010-12-29 | University Of The Witwatersrand, Johannesburg | Proton exchange membrane fuel cell |
| CN102452646B (en) * | 2010-10-26 | 2013-10-09 | 清华大学 | Method for preparing hydrophilic carbon nanotube film |
| CN103887518B (en) * | 2014-03-26 | 2016-08-17 | 清华大学 | A kind of ordered polymer membrane electrode from humidification |
| CN104779400B (en) * | 2015-03-31 | 2017-07-07 | 华北电力大学 | A kind of preparation method of the modified carbon nano-tube for PEM |
| CN105655607A (en) * | 2016-02-01 | 2016-06-08 | 中国科学院福建物质结构研究所 | High-platinum base-loaded carbon nano tube nanocatalyst and preparation method thereof |
| CN106543460B (en) * | 2016-12-06 | 2020-04-28 | 复旦大学 | CNT@Fe3O4@ C modified polymer hybrid proton exchange membrane and preparation method thereof |
| CN107308824B (en) * | 2017-08-25 | 2020-06-16 | 南开大学 | Preparation method of sulfonic acid type cation exchange membrane |
| CN110510599B (en) * | 2019-09-10 | 2022-08-09 | 新疆大学 | Thin-wall amorphous carbon nanotube and preparation method and application thereof |
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