CN103531831B - Temperature proton exchange film material and preparation method thereof in a kind of soda acid type aminopolyphosphonic acid polysiloxanes - Google Patents
Temperature proton exchange film material and preparation method thereof in a kind of soda acid type aminopolyphosphonic acid polysiloxanes Download PDFInfo
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Abstract
The invention provides temperature proton exchange film material and preparation method thereof in a kind of soda acid type aminopolyphosphonic acid polysiloxanes, the raw material preparing this membrane material comprises organic phospho acid, aminoalkoxysilane, and the mol ratio of described raw material is organic phospho acid: aminoalkoxysilane=1:2-1:4.In this soda acid type aminopolyphosphonic acid polysiloxanes, temperature proton exchange film material reaction condition is gentle, and bonding phosphorus acid content is high, and can effectively suppress phosphoric acid to ooze out, and proton conductivity is high, functional under middle gentle low humidity service condition.
Description
Technical field
The invention belongs to fuel cell manufacturing technology field, the fuel cell being specifically related to temperature proton exchange film material and preparation method thereof in a kind of soda acid type aminopolyphosphonic acid polysiloxanes and using this material to prepare.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is environmentally friendly, and has the advantages such as volume is little, quality is light, and being suitable for use as the portable power source of walkie electronic apparatus, is the focus of current energy research field and exploitation.Proton exchange membrane (PEM) is the important component part of Proton Exchange Membrane Fuel Cells, and it not only plays a part isolation fuel (as CO) and oxidant prevents them from directly reacting, and more plays electrolytical effect.The power output of the performance appreciable impact PEMFC of proton exchange membrane and battery efficiency.Current PEMFC generally adopts Pt or Pt alloy to make catalyst, and the perfluoro sulfonic acid membrane (PFSI) that to adopt with Nafion film be representative makes exchange membrane.Perfluoro sulfonic acid membrane (PFSI) performance when working temperature is about 80 DEG C is comparatively excellent, but in this temperature range, catalyst is more to CO absorption in fuel, makes catalyst poisoning, thus significantly reduces the performance of battery.One of effective ways of head it off are more than the working temperatures to 100 DEG C improving battery.Improve the dynamics that the working temperature of Proton Exchange Membrane Fuel Cells also can improve the especially cathodic oxygen reduction reaction of negative and positive the two poles of the earth, and then improve the operating efficiency of battery.And the conductivity of existing perfluoro sulfonic acid membrane is strongly depend on moisture content, limit it higher than the application at boiling point (100 DEG C) temperature of water.Therefore, the developmental research of middle temperature (120-180 DEG C) spendable proton exchange membrane material becomes the focus of current PEMFC developmental research.
Oxyacid is as higher from degree of dissociation due to it in phosphoric acid, sulfuric acid, perchloric acid, still demonstrates good proton conductive in anhydrous conditions.Wherein liquid phosphoric acid has very high from degree of dissociation (7.4%), has a large amount of H in system
+exist, its diffusion rate is about 2 × 10
-5cm
2/ s, comparatively other acid system is high a lot, is a kind ofly high proton solubility and high proton transmission rate to be combined to obtain the proton carrier of near ideal.Phosphoric acid, as the liquid electrolyte of fuel cell, when the working temperature of about phosphoric acid fuel cell 150-200 DEG C, still has higher proton conducting ability.So the proton conductive unit being used as middle temperature proton exchange film with phosphoric acid is a selection preferably.Phosphoric acid mixes in high temperature-resistant polymer fertile material and has prepared middle temperature proton exchange film by domestic and international many researchers, such as phosphate-doped polybenzimidazoles proton exchange membrane, this material still has very high proton conductivity under low humidity with the environment reaching 200 DEG C, because cost is high, so its commercialization is restricted, and the Interaction Force of phosphoric acid and polybenzimidazoles is more weak, oozing out of phosphoric acid can be caused, affect the long-term behaviour of fuel cell.Therefore, how being anchored on macromolecule matrix by phosphoric acid is next step research emphasis of this kind of middle temperature proton exchange film.(the Electrochimica Acta. such as the researcher Masaki Kato of Min Gu room university of Japan, 2007,52,5924) by hydroxyl and γ-(2 of PHOSPHONACETIC, ethoxy phosphoric acid etc., 3-epoxy third oxygen) the epoxide group open loop bonding of propyl trimethoxy silicane (GPTMS) prepares hybrid inorganic-organic proton conductive membrane, compared with GPTMS compound phosphoric acid film, the phosphoric acid burst size of this film in water greatly reduces, but because the C-O-P key stability of bonding is not good, at high temperature easily be hydrolyzed, have a strong impact on its useful life.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, fuel cell temperature proton exchange film material and preparation method thereof in a kind of soda acid type aminopolyphosphonic acid polysiloxanes being provided and using this material to prepare, the method reaction condition is gentle, technique is simple, prepared material phosphoric acid content is high, can phosphoric acid be effectively suppressed to ooze out, and excellent in mechanical performance, in corresponding, temperature proton exchange film proton conductivity is high, functional under middle temperature low humidity service condition.
The technical scheme that solution the technology of the present invention problem adopts is to provide temperature proton exchange film material in a kind of soda acid type aminopolyphosphonic acid polysiloxanes, the raw material preparing temperature proton exchange film material in this soda acid type aminopolyphosphonic acid polysiloxanes comprises organic phospho acid, aminoalkoxysilane, and the mol ratio of described raw material is organic phospho acid: aminoalkoxysilane=1:2-1:4.
Crosslinked is a kind of important method improving polymer physics, chemical property, and suitably crosslinked polymer all increases than corresponding linear polymer in mechanical strength, heat-resisting (trembling with fear) property, chemical stability etc.And to prepare soda acid type hybridized polymer film be one of crosslinked method.Phosphorus (phosphine) acid is a kind of material of both sexes, be proton donor and proton acceptor, also there is very high electric double layer constant, thus there is very high proton from disengaging ability, it can as the protogenic group of product, by formation and the fracture of intermolecular dynamic hydrogen bond, proton has been jumped proton transfer between phosphoric acid molecules, is a kind of ideal proton conduction unit carrying out proton transfer under high temperature low humidity conditions.Take phosphoric acid as proton conductive group, polysiloxanes is agent structure, the cooperative effect between phosphorus and nitrogen can be utilized, the formation of phosphoric acid proton defect can be accelerated, namely the disengaging certainly of phosphoric acid, assists the formation of hydrogen bond network between phosphoric acid molecules simultaneously, forms continuous print hydrogen bond network, by formation and the fracture of continuous hydrogen bond, realize the transmission of proton between phosphoric acid molecules, greatly reduce the dependence to water, the object of the low humidity that reaches a high temperature conduction.
Preferably, described organic phospho acid is the one in Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid or ethylenediamine tetramethylene phosphonic acid.
Preferably, described aminoalkoxysilane is the one in 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane.Amino in aminoalkoxysilane can with organic phospho acid generation acid-base reaction, play the effect of access phosphonic acids, and aminoalkoxysilane can be hydrolyzed formation Si-O network configuration.
Present invention also offers the preparation method of temperature proton exchange film material in above-mentioned soda acid type aminopolyphosphonic acid polysiloxanes, this preparation method comprises the following steps:
(1) be dissolved with machine phosphonic acid: be at room temperature dissolved in solvent by the organic phospho acid of 1 molar part, obtain organic phospho acid solution;
(2) aminoalkoxysilane is dripped: be added drop-wise in step (1) gained organic phospho acid solution with the speed of 1-2 drop/sec by the aminoalkoxysilane of 2-4 molar part at 0-20 DEG C, obtain reactant mixed liquor;
(3) be incubated: step (2) gained reactant mixed liquor is stirred and is incubated 24-48 hour at 0-20 DEG C, obtains nitrogenous polyphosphonic acid siloxane sol;
(4) film forming: nitrogenous for step (3) gained polyphosphonic acid siloxane sol is also dry through gelation process, obtains temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
In step (3) ,-P (O) (OH) on organic phospho acid
2-NH on group and aminoalkoxysilane
2there is acid-base neutralization reaction in group, reaction mechanism is as follows in water:
Above-mentioned steps (3) reaction generates nitrogenous polyphosphonic acid siloxane sol, soda acid salinization reaction not only introduces network configuration, and due to intermolecular hydrogen bonding effect, make that the membrane material mechanical stability of preparation is good, pliability is high, there is less swellability and Small molecular permeability simultaneously.
In order to avoid causing system temperature to raise the implode causing siloxanes due to neutralization reaction heat release, need to control reaction temperature at 0-20 DEG C.
Preferably, the one that to be organic phospho acid be in Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid or ethylenediamine tetramethylene phosphonic acid of organic phospho acid described in step (1).
Preferably, aminoalkoxysilane described in step (2) is the one in 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane.
Preferably, the vacuumize 24-48 hour at 0.02-0.08MPa vacuum degree, 40-60 DEG C again after comprising at room temperature ageing 3-5 days of gelation process described in step (4).
At room temperature, the sour environment provided by organic phospho acid, makes the Si-OC in the nitrogenous polyphosphonic acid siloxane sol of step (3) gained
2h
5be hydrolyzed in water, deviate from ethanol, generate Si-OH, produce intermolecular dehydrating condensation afterwards, form Si-O-Si cross-linked network structure, reaction mechanism is as follows:
Obtain the soda acid type aminopolyphosphonic acid polysiloxanes of gelation, final drying obtains temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The present invention also provides the fuel cell that in above-mentioned soda acid type aminopolyphosphonic acid polysiloxanes prepared by temperature proton exchange film material, namely comprises the exchange membrane of battery prepared by temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes prepared according to the above preparation method.
The invention has the beneficial effects as follows: use the method being simple and easy to realize to prepare temperature proton exchange film material in fuel cell soda acid type aminopolyphosphonic acid polysiloxanes, the compatibility of phosphoric acid and polymer is strengthened by cross-linking reaction, phosphoric acid molecules is stoped to ooze out, improve phosphorus acid content in exchange membrane material, in the proton conductivity improving fuel battery proton exchange film material and resistance to middle temperature stability, there is marked improvement, by the proton exchange membrane material made by the present invention, under middle temperature (120 DEG C) and low humidity (50% relative humidity) condition, proton conductivity can reach 0.059-0.072S/cm, and temperature proton exchange film tensile strength of material comparatively large (27.5-31.9MPa) in this soda acid type aminopolyphosphonic acid polysiloxanes, there is excellent toughness, thermal stability and chemical stability.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
The embodiment of the present invention provides a kind of and has temperature proton exchange film material in the fuel cell soda acid type aminopolyphosphonic acid polysiloxanes of high proton conductivity.
Embodiment one
Under room temperature (20 DEG C), the deionized water of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the Amino Trimethylene Phosphonic Acid of 2.99g is put into there-necked flask, be stirred to Amino Trimethylene Phosphonic Acid with the speed of 600r/min to dissolve completely, obtain Amino Trimethylene Phosphonic Acid solution; Again there-necked flask is put into frozen water mixing bath, drip the 3-aminopropyl triethoxysilane (mol ratio Amino Trimethylene Phosphonic Acid: 3-aminopropyl triethoxysilane=1:4) of 8.85g with the speed of 1 drop/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 24h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 3 days, then in 0.02MPa vacuum degree, vacuumize 1 day at 40 DEG C, dry successively subsequently to dry at 3 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, after cooling, Product Films is peeled off from polytetrafluoroethylene mould, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
Test through electrochemical workstation, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:0.74,120 DEG C, to test proton conductivity under being 25% condition be 0.061S/cm to relative humidity, ion exchange capacity is 0.64mg/mol, hot strength is 30.2Mpa, linear swelling coefficient is 6.24%, and water absorption rate is 14.8%, and stability in use is good at 215 DEG C.
Embodiment two
Under room temperature (20 DEG C), the deionized water of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the hydroxy ethylene diphosphonic acid of 2.06g is put into there-necked flask, be stirred to hydroxy ethylene diphosphonic acid with the speed of 700r/min to dissolve completely, obtain hydroxy ethylene diphosphonic acid solution; There-necked flask is put into 8 DEG C of cold baths again, drip the 3-aminopropyl triethoxysilane (mol ratio hydroxy ethylene diphosphonic acid: 3-aminopropyl triethoxysilane=1:4) of 8.85g with the speed of 1 drop/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 24h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 4 days, then in 0.04MPa vacuum degree, vacuumize 1 day at 50 DEG C, dry successively subsequently to dry at 4 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The method of testing same with embodiment one is adopted to test temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes of the present embodiment gained, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:0.93,120 DEG C, to test proton conductivity under being 25% condition be 0.063S/cm to relative humidity, ion exchange capacity is 0.70mg/mol, hot strength is 29.9Mpa, linear swelling coefficient is 7.81%, water absorption rate is 15.0%, and stability in use is good at 215 DEG C.
Embodiment three
Under room temperature (20 DEG C), the deionized water of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the hydroxy ethylene diphosphonic acid of 3.09g is put into there-necked flask, be stirred to hydroxy ethylene diphosphonic acid with the speed of 800r/min to dissolve completely, obtain hydroxy ethylene diphosphonic acid solution; Again there-necked flask is put into frozen water mixing bath, drip the 3-aminopropyl trimethoxysilane (mol ratio hydroxy ethylene diphosphonic acid: 3-aminopropyl trimethoxysilane=1.5:4) of 7.17g with the speed of 2 drops/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 24h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 3 days, then in 0.06MPa vacuum degree, vacuumize 1 day at 60 DEG C, dry successively subsequently to dry at 5 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The method of testing same with embodiment one is adopted to test temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes of the present embodiment gained, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:0.73,120 DEG C, to test proton conductivity under being 25% condition be 0.059S/cm to relative humidity, ion exchange capacity is 0.58mg/mol, hot strength is 31.9Mpa, linear swelling coefficient is 5.48%, water absorption rate is 13.1%, and stability in use is good at 210 DEG C.
Embodiment four
Under room temperature (20 DEG C), the deionized water of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the ethylenediamine tetramethylene phosphonic acid of 4.36g is put into there-necked flask, be stirred to ethylenediamine tetramethylene phosphonic acid with the speed of 800r/min to dissolve completely, obtain ethylenediamine tetramethylene phosphonic acid solution; There-necked flask is put into 5 DEG C of cold baths again, drip the 3-aminopropyl triethoxysilane (mol ratio ethylenediamine tetramethylene phosphonic acid: 3-aminopropyl triethoxysilane=1:4) of 8.85g with the speed of 2 drops/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 24h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 3 days, then in 0.08MPa vacuum degree, vacuumize 1 day at 60 DEG C, dry successively subsequently to dry at 6 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The method of testing same with embodiment one is adopted to test temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes of the present embodiment gained, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:1.73,120 DEG C, to test proton conductivity under being 25% condition be 0.072S/cm to relative humidity, ion exchange capacity is 0.79mg/mol, hot strength is 27.5Mpa, linear swelling coefficient is 9.76%, water absorption rate is 16.6%, and stability in use is good at 220 DEG C.
Embodiment five
Under room temperature (20 DEG C), the deionized water of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the Amino Trimethylene Phosphonic Acid of 4.49g is put into there-necked flask, be stirred to Amino Trimethylene Phosphonic Acid with the speed of 700r/min to dissolve completely, obtain Amino Trimethylene Phosphonic Acid solution; There-necked flask is put into 15 DEG C of cold baths again, drip the 3-aminopropyl trimethoxysilane (mol ratio Amino Trimethylene Phosphonic Acid: 3-aminopropyl trimethoxysilane=1.5:4) of 7.17g with the speed of 1 drop/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 24h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 3 days, then in 0.05MPa vacuum degree, vacuumize 1 day at 50 DEG C, dry successively subsequently to dry at 6 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The method of testing same with embodiment one is adopted to test temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes of the present embodiment gained, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:1.10,120 DEG C, to test proton conductivity under being 25% condition be 0.064S/cm to relative humidity, ion exchange capacity is 0.75mg/mol, hot strength is 29.7Mpa, linear swelling coefficient is 8.12%, water absorption rate is 15.2%, and stability in use is good at 230 DEG C.
Embodiment six
Under room temperature (20 DEG C), the deionized water of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the Amino Trimethylene Phosphonic Acid of 5.98g is put into there-necked flask, be stirred to Amino Trimethylene Phosphonic Acid with the speed of 800r/min to dissolve completely, obtain Amino Trimethylene Phosphonic Acid solution; There-necked flask is put into 20 DEG C of cold baths again, drip the 3-aminopropyl triethoxysilane (mol ratio Amino Trimethylene Phosphonic Acid: 3-aminopropyl triethoxysilane=1:2) of 8.85g with the speed of 2 drops/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 12h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 2 days, then in 0.08MPa vacuum degree, vacuumize 1 day at 60 DEG C, dry successively subsequently to dry at 5 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The method of testing same with embodiment one is adopted to test temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes of the present embodiment gained, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:1.43,120 DEG C, to test proton conductivity under being 25% condition be 0.068S/cm to relative humidity, ion exchange capacity is 0.77mg/mol, hot strength is 29.3Mpa, linear swelling coefficient is 8.91%, water absorption rate is 16.1%, and stability in use is good at 225 DEG C.
Embodiment seven
Under room temperature (20 DEG C), the ethanol of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the Amino Trimethylene Phosphonic Acid of 2.99g is put into there-necked flask, be stirred to Amino Trimethylene Phosphonic Acid with the speed of 800r/min to dissolve completely, obtain Amino Trimethylene Phosphonic Acid solution; There-necked flask is put into 10 DEG C of cold baths again, drip the 3-aminopropyl triethoxysilane (mol ratio Amino Trimethylene Phosphonic Acid: 3-aminopropyl triethoxysilane=1:4) of 8.85g with the speed of 2 drops/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 12h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 2 days, then in 0.08MPa vacuum degree, vacuumize 1 day at 60 DEG C, dry successively subsequently to dry at 5 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The method of testing same with embodiment one is adopted to test temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes of the present embodiment gained, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:0.74,120 DEG C, to test proton conductivity under being 25% condition be 0.062S/cm to relative humidity, ion exchange capacity is 0.65mg/mol, hot strength is 30.0Mpa, linear swelling coefficient is 6.17%, water absorption rate is 14.5%, and stability in use is good at 215 DEG C.
Embodiment eight
Under room temperature (20 DEG C), the ethanol of 20mL is positioned in the there-necked flask being furnished with puddler and thermometer, the Amino Trimethylene Phosphonic Acid of 5.98g is put into there-necked flask, be stirred to Amino Trimethylene Phosphonic Acid with the speed of 800r/min to dissolve completely, obtain Amino Trimethylene Phosphonic Acid solution; Again there-necked flask is put into frozen water mixing bath, drip the 3-aminopropyl triethoxysilane (mol ratio Amino Trimethylene Phosphonic Acid: 3-aminopropyl triethoxysilane=1:2) of 8.85g with the speed of 2 drops/sec in there-necked flask, keep in the process dripped stirring, and drip rear continuation and stir 12h, obtain nitrogenous polyphosphonic acid siloxane sol.The nitrogenous polyphosphonic acid siloxane sol obtained is poured in polytetrafluoroethylene mould, at room temperature ageing 2 days, then in 0.08MPa vacuum degree, vacuumize 1 day at 60 DEG C, dry successively subsequently to dry at 5 hours, 120 DEG C to dry at 150 DEG C for 2 hours at 80 DEG C and within 2 hours, obtain dry Product Films, obtain temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
The method of testing same with embodiment one is adopted to test temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes of the present embodiment gained, in soda acid type aminopolyphosphonic acid polysiloxanes made by the present embodiment, in temperature proton exchange film material, silicon phosphorus mol ratio is Si:P=1:1.41,120 DEG C, to test proton conductivity under being 25% condition be 0.066S/cm to relative humidity, ion exchange capacity is 0.78mg/mol, hot strength is 29.1Mpa, linear swelling coefficient is 8.78%, water absorption rate is 16.3%, and stability in use is good at 220 DEG C.
By the above detailed description to the embodiment of the present invention, can understand and the invention solves in routine that temperature proton exchange film material technology is complicated, phosphorus acid content is few and phosphoric acid easily oozes out and causes low, the short-life problem of fuel battery proton exchange film conductivity, in gained proton exchange membrane material, Si:P ratio is 1:0.73-1:1.73, and proton conductivity can reach 0.059-0.072S/cm.And ability more than 210 DEG C high temperature, under middle temperature 120 DEG C, relative humidity 25% condition, serviceability is stablized.Combination property is better than the middle temperature proton exchange film material prepared in prior art.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (4)
1. prepare a method for temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes, it is characterized in that comprising the following steps:
(1) be dissolved with machine phosphonic acid: be at room temperature dissolved in solvent by the organic phospho acid of 1 molar part, obtain organic phospho acid solution;
(2) aminoalkoxysilane is dripped: be added drop-wise in step (1) gained organic phospho acid solution with the speed of 1-2 drop/sec by the aminoalkoxysilane of 2-4 molar part at 0-20 DEG C, obtain reactant mixed liquor;
(3) be incubated: step (2) gained reactant mixed liquor is stirred and is incubated 24-48 hour at 0-20 DEG C, obtains nitrogenous polyphosphonic acid siloxane sol;
(4) film forming: nitrogenous for step (3) gained polyphosphonic acid siloxane sol is also dry through gelation process, obtains temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes.
2. the method preparing temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes according to claim 1, it is characterized in that organic phospho acid described in step (1) is the one in Amino Trimethylene Phosphonic Acid, hydroxy ethylene diphosphonic acid or ethylenediamine tetramethylene phosphonic acid, described solvent is water or ethanol, and aminoalkoxysilane described in step (2) is the one in 3-aminopropyl triethoxysilane or 3-aminopropyl trimethoxysilane.
3. the method preparing temperature proton exchange film material in soda acid type aminopolyphosphonic acid polysiloxanes according to claim 1, it is characterized in that the described gelation process of step (4) comprise at room temperature ageing 3-5 days after vacuumize 24-48 hour at 0.02-0.08MPa vacuum degree, 40-60 DEG C again.
4. a proton exchanging film fuel battery, is characterized in that comprising temperature proton exchange film material in the soda acid type aminopolyphosphonic acid polysiloxanes prepared according to the arbitrary described preparation method of claim 1-3 and prepares the proton exchange membrane of battery.
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| CN104485470B (en) * | 2014-12-16 | 2017-03-08 | 武汉理工大学 | A kind of polysiloxanes polyphosphonic acid doping shitosan high temperature proton exchange film and preparation method thereof |
| CN104779407B (en) * | 2015-04-27 | 2017-03-01 | 武汉理工大学 | A kind of nitrogenous polyphosphonic acid based polysiloxane/Nafion bilayer PEM and preparation method thereof |
| CN105037733B (en) * | 2015-05-29 | 2017-11-17 | 武汉理工大学 | A kind of phosphoric acid radical siloxane high temperature proton exchange film of hydrolysis-stable and preparation method thereof |
| TWI564325B (en) * | 2015-12-24 | 2017-01-01 | 國立清華大學 | Proton exchange membrane and manufacturing method thereof |
| CN105895943B (en) * | 2016-05-03 | 2018-09-14 | 武汉理工大学 | A kind of phosphonic-acid grafted polybenzimidazoles high temperature proton exchange film and preparation method thereof |
| CN107799794B (en) * | 2017-10-19 | 2021-02-09 | 武汉氢阳能源有限公司 | High-temperature proton exchange membrane based on organic phosphonic acid and preparation method and application thereof |
| CN114824394B (en) * | 2021-01-29 | 2024-01-26 | 武汉氢阳能源有限公司 | Modified inorganic heteropolyacid composite high-temperature proton exchange membrane and preparation method thereof |
| CN114824392B (en) * | 2021-01-29 | 2024-01-30 | 武汉氢阳能源有限公司 | Long-chain organic amine modified organic proton conductor composite proton exchange membrane and preparation method thereof |
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