CN101376717A - Preparation of nano inorganic doped perfluorosulfonated compound film - Google Patents
Preparation of nano inorganic doped perfluorosulfonated compound film Download PDFInfo
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- CN101376717A CN101376717A CNA2008101369287A CN200810136928A CN101376717A CN 101376717 A CN101376717 A CN 101376717A CN A2008101369287 A CNA2008101369287 A CN A2008101369287A CN 200810136928 A CN200810136928 A CN 200810136928A CN 101376717 A CN101376717 A CN 101376717A
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Abstract
The invention discloses a preparation method of a compound film of perfluorinated sulfonic acid doped with a nano mineral which relates to a preparation method of the compound film of perfluorinated sulfonic acid doped with the nano mineral. The problem of poor stability of the compound film prepared in the existing preparation method of the compound film of perfluorinated sulfonic acid doped with the nano mineral is solved. The first method of the invention is carried out according to the following steps: I, a perfluorinated sulfonic acid film is pre-treated; II, the nano mineral is doped, thus obtaining the compound film of perfluorinated sulfonic acid doped with the nano mineral. The second method of the invention is carried out according to the following steps: I, the perfluorinated sulfonic acid film is pre-treated; II, the nano mineral is doped, thus obtaining the compound film of perfluorinated sulfonic acid doped with the nano mineral. The third method of the invention is carried out as follows: I, the perfluorinated sulfonic acid film is pre-treated; II, the nano mineral is doped, thus obtaining the compound film of perfluorinated sulfonic acid doped with the nano mineral. The compound film prepared by the invention has the advantages of good thermal stability, acid stability and comprehensive indexes as well as high conductive rate.
Description
Technical field
The present invention relates to the preparation method of inorganics doped perfluorinated sulfonic acid composite membrane.
Background technology
The preparation method of at present inorganics doped perfluorinated sulfonic acid composite membrane mainly contains two kinds.The one, adopt sol-gel process at first to prepare nano-inorganic substance, be dispersed in then in the perfluorinated sulfonic acid coating solution and form mixed solution, adopt the double teeming membrane method to prepare composite membrane again; It two is to adopt the original position composite methods, is about at first swelling in methyl alcohol of perfluoro sulfonic acid membrane, then the inorganics presoma is penetrated in the film after the swelling, and the formation composite membrane is hydrolyzed.The shortcoming of first method is that the thermostability of double teeming film descends, and the homodisperse of the inorganic particulate that is difficult to guarantee to mix.The problem that second method exists is the single composition material that the inorganic particulate of in-situ hydrolysis formation is in noncrystalline state often, less stable, in use cause component to run off, composite membrane generation moderate finite deformation, and the polycomponent inorganic materials is difficult to adopt this method and perfluoro sulfonic acid membrane film to form composite membrane.
Summary of the invention
The present invention exists the thermostability of double teeming film to descend in order to solve the composite membrane that sol-gel method is prepared among the preparation method who has inorganics doped perfluorinated sulfonic acid composite membrane now, the problem that in-situ compositing exists is the single composition material that the inorganic particulate of in-situ hydrolysis formation is in noncrystalline state often, the problem of poor stability, and the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance is provided.
First kind of method for preparing the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of the present invention carried out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, the dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, put into the metal-nitrate solutions that concentration is 1mol/L and the mixed solution of methyl alcohol again and flood 30min～120min, wherein metal-nitrate solutions and methyl alcohol are according to the mixed of volume ratio 1:1～5, put into volumetric concentration then and be 16%～50% ammoniacal liquor and flood 3h, taking out the back cleans 3～5 times with dehydrated alcohol, then at 80 ℃ of dry 16h, again composite membrane is placed the stainless steel autoclave of teflon lined, add deionized water, the baking oven of putting into 120 ℃～180 ℃ heated 1～24 hour; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance; Wherein the solute of the metal-nitrate solutions in the step 2 is Mg (NO
3)
2, Al (NO
3)
3, Ga (NO
3)
3, In (NO
3)
3, La (NO
3)
3, Y (NO
3)
3Or Ce (NO
3)
3
Be doped to inorganics in the perfluoro sulfonic acid membrane by the decision of the solute of the metal-nitrate solutions in the step 2 in the first method of the present invention, adulterated inorganics is MgO, Al
2O
3, Ga
2O
3, In
2O
3, La
2O
3, Y
2O
3Or CeO
2, corresponding one by one with the solute of metal-nitrate solutions in the step 2.
Second kind of method for preparing the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of the present invention carried out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, and putting into concentration again is the Ca (NO of 1mol/L
3)
2Flood 30min～120min in the mixed solution of solution and methyl alcohol, wherein Ca (NO
3)
2Solution and methyl alcohol are according to the mixed of volume ratio 1:1～5, taking out the back cleans 3～5 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, dry 2h under 100 ℃ condition then, composite membrane is placed the stainless steel autoclave of teflon lined, adding concentration is the (NH of 1mol/L again
4)
2HPO
4Solution, pH value to 8～12 of regulator solution, the baking oven of putting into 120 ℃～180 ℃ heated 1～10 day; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
That second method of the present invention prepares is nanometer Ca
5(PO
4)
3The adulterated perfluorinated sulfonic acid composite membrane of OH.
The third method for preparing the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of the present invention is carried out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, puts into the TiCl that concentration is 1mol/L again
4Flood 30min～120min in the mixed solution of solution and methyl alcohol, wherein TiCl
4Solution and methyl alcohol are according to the mixed of volume ratio 1:1～5, put into volumetric concentration then and be 16%～50% ammoniacal liquor and flood 3h, taking out the back cleans 3～5 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, composite membrane is placed the stainless steel autoclave of teflon lined, adding concentration is the Ba (OH) of 1mol/L again
2Solution, pH value to 8～14 of regulator solution, the baking oven of putting into 120 ℃～180 ℃ heated 1～10 day; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
That the third method of the present invention prepares is nanometer BaTiO
3Adulterated perfluorinated sulfonic acid composite membrane.
Three kinds of methods of the present invention all have the following advantages: the Heat stability is good of the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance of 1, preparing; 2, adulterated inorganics is crystal form, and the interaction of crystallization phases inorganics and perfluoro sulfonic acid membrane branched group enhancing, thereby improves the thermal stability and the acid acceptance energy of composite membrane; Specific conductivity height, the overall target of the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance of 3, preparing are good.
Description of drawings
Fig. 1 is the XRD contrast spectrogram of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 19 preparations and the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the XRD spectra of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 19 preparations, and 2 lines are the XRD spectra of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 2 is the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 19 preparations and the infrared contrast spectrogram of the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the infrared spectrum of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 19 preparations, and 2 lines are the infrared spectrum of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 3 is the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 19 preparations and the specific conductivity test comparison figure of the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the conductivity map of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 19 preparations, and 2 lines are the conductivity map of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 4 is the XRD contrast spectrogram of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 32 preparations and the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the XRD spectra of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 32 preparations, and 2 lines are the XRD spectra of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 5 is the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 32 preparations and the infrared contrast spectrogram of the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the infrared spectrum of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 32 preparations, and 2 lines are the infrared spectrum of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 6 is the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 32 preparations and the specific conductivity test comparison figure of the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the conductivity map of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 32 preparations, and 2 lines are the conductivity map of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 7 is the XRD contrast spectrogram of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 48 preparations and the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the XRD spectra of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 48 preparations, and 2 lines are the XRD spectra of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 8 is the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 48 preparations and the infrared contrast spectrogram of the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the infrared spectrum of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 48 preparations, and 2 lines are the infrared spectrum of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation; Fig. 9 is the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 48 preparations and the specific conductivity test comparison figure of the doping inorganics perfluorinated sulfonic acid composite membrane that in-situ compositing prepares, wherein 1 line is the conductivity map of the dopen Nano inorganics perfluorinated sulfonic acid composite membrane of embodiment 48 preparations, and 2 lines are the conductivity map of the doping inorganics perfluorinated sulfonic acid composite membrane of in-situ compositing preparation.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment prepares the method for the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance and carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, the dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, put into the metal-nitrate solutions that concentration is 1mol/L and the mixed solution of methyl alcohol again and flood 30min～120min, wherein metal-nitrate solutions and methyl alcohol are according to the mixed of volume ratio 1:1～5, put into volumetric concentration then and be 16%～50% ammoniacal liquor and flood 3h, taking out the back cleans 3～5 times with dehydrated alcohol, then at 80 ℃ of dry 16h, again composite membrane is placed the stainless steel autoclave of teflon lined, add deionized water, the baking oven of putting into 120 ℃～180 ℃ heated 1～24 hour; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance; Wherein the solute of the metal-nitrate solutions in the step 2 is Mg (NO
3)
2, Al (NO
3)
3, Ga (NO
3)
3, In (NO
3)
3, La (NO
3)
3, Y (NO
3)
3Or Ce (NO
3)
3
Be doped to inorganics in the perfluoro sulfonic acid membrane by the decision of the solute of the metal-nitrate solutions in the step 2 in the present embodiment, adulterated inorganics is MgO, Al
2O
3, Ga
2O
3, In
2O
3, La
2O
3, Y
2O
3Or CeO
2, corresponding one by one with the solute of metal-nitrate solutions in the step 2.
In the step 2 of present embodiment composite membrane is placed the stainless steel autoclave back of teflon lined to add deionized water, the add-on of deionized water is not as the criterion can there not to be composite membrane.
Embodiment two: the difference of present embodiment and embodiment one is: in the step 1 perfluoro sulfonic acid membrane put into mass concentration and be 4% hydrogen peroxide solution and soak.Other step and parameter are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one is: the perfluoro sulfonic acid membrane of in the step 1 hydrogen peroxide dipping being crossed deionized water rinsing 4 times.Other step and parameter are identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is: the perfluoro sulfonic acid membrane that in the step 1 sulfuric acid was soaked deionized water rinsing 4 times.Other step and parameter are identical with embodiment one.
Embodiment five: the difference of present embodiment and embodiment one is: put into the metal-nitrate solutions that concentration is 1mol/L and the mixed solution of methyl alcohol in the step 2 and flood 50min～100min, wherein metal-nitrate solutions and methyl alcohol are according to the mixed of volume ratio 1:2～4.Other step and parameter are identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is: put into the metal-nitrate solutions that concentration is 1mol/L and the mixed solution of methyl alcohol in the step 2 and flood 80min, wherein metal-nitrate solutions and methyl alcohol are according to the mixed of volume ratio 1:3.Other step and parameter are identical with embodiment one.
Embodiment seven: the difference of present embodiment and embodiment one is: put into volumetric concentration in the step 2 and be 20%～45% ammoniacal liquor and flood.Other step and parameter are identical with embodiment one.
Embodiment eight: the difference of present embodiment and embodiment one is: put into volumetric concentration in the step 2 and be 25%～40% ammoniacal liquor and flood.Other step and parameter are identical with embodiment one.
Embodiment nine: the difference of present embodiment and embodiment one is: put into volumetric concentration in the step 2 and be 30%～35% ammoniacal liquor and flood.Other step and parameter are identical with embodiment one.
Embodiment ten: the difference of present embodiment and embodiment one is: put into volumetric concentration in the step 2 and be 32% ammoniacal liquor and flood.Other step and parameter are identical with embodiment one.
Embodiment 11: the difference of present embodiment and embodiment one is: take out the back in the step 2 and clean 4 times with dehydrated alcohol from ammoniacal liquor.Other step and parameter are identical with embodiment one.
Embodiment 12: the difference of present embodiment and embodiment one is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, add 40mL～120mL deionized water.Other step and parameter are identical with embodiment one.
Embodiment 13: the difference of present embodiment and embodiment one is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, add 60mL～100mL deionized water.Other step and parameter are identical with embodiment one.
Embodiment 14: the difference of present embodiment and embodiment one is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, add the 80mL deionized water.Other step and parameter are identical with embodiment one.
Embodiment 15: the difference of present embodiment and embodiment one is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, add the 80mL deionized water.
Embodiment 16: the difference of present embodiment and embodiment one is: the baking oven of putting into 130 ℃～170 ℃ in the step 2 heated 4～21 hours.Other step and parameter are identical with embodiment one.
Embodiment 17: the difference of present embodiment and embodiment one is: the baking oven of putting into 140 ℃～160 ℃ in the step 2 heated 7～18 hours.Other step and parameter are identical with embodiment one.
Embodiment 18: the difference of present embodiment and embodiment one is: the baking oven of putting into 150 ℃ in the step 2 heated 12 hours.Other step and parameter are identical with embodiment one.
Embodiment 19: present embodiment prepares the method for the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance and carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 4% the hydrogen peroxide solution, take out back deionized water rinsing 4 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 4 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 4 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, the dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, put into the metal-nitrate solutions that concentration is 1mol/L and the mixed solution of methyl alcohol again and flood 100min, wherein metal-nitrate solutions and methyl alcohol are according to the mixed of volume ratio 1:3, put into volumetric concentration then and be 30% ammoniacal liquor and flood 3h, taking out the back cleans 4 times with dehydrated alcohol, then at 80 ℃ of dry 16h, again composite membrane is placed the stainless steel autoclave of teflon lined, add the 100mL deionized water, the baking oven of putting into 150 ℃ heated 14 hours; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance; Wherein the solute of the metal-nitrate solutions in the step 2 is Ce (NO
3)
3
That present embodiment prepares is nano Ce O
2Adulterated perfluorinated sulfonic acid composite membrane.
Nano Ce O with the present embodiment preparation
2Adulterated perfluorinated sulfonic acid composite membrane carries out test performance, need before the performance test film of preparing is carried out cleaning pretreatment: with composite membrane deionized water drip washing 5 times of present embodiment preparation, the sulphuric acid soln of putting into 80 ℃, concentration then and be 0.1mol/L heats 30min, use deionized water rinsing once more 5 times, 80 ℃ of heating in water bath and washing three times in deionized water at last, each half an hour, after handling totally, film carries out following performance test:
1, the initial heat decomposition temperature of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that present embodiment is prepared is 335 ℃, and what adopt existing original position composite methods preparation is 320 ℃, and the Heat stability is good of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that the method for present embodiment is prepared is described.
2, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the test of water content, test condition is as follows: the water content difference of composite membrane calculates in the of poor quality of hygrometric state and dry state according to film, above-mentioned composite membrane is flooded 12h respectively in 25 ℃ of deionized waters, blot the water on film surface with filter paper, its weight in wet base of weighing W
WetThen with film its dry weight of weighing W behind 110 ℃ of baking 16h
DryThe massfraction of water is [100 (W in the film
Wet-W
Dry)/W
Wet] %.Testing out present embodiment, to prepare the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance water content be 165%, existing method be 55%, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that the present embodiment preparation is described has the ability of higher maintenance water, thereby guarantees that composite membrane has proton conductivity preferably.
3, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out XRD and examination of infrared spectrum, the XRD test result as shown in Figure 1, the examination of infrared spectrum result as shown in Figure 2, from Fig. 1 and Fig. 2 as can be seen, the adulterated inorganics of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation is crystal form, and the interaction of crystallization phases inorganics and perfluoro sulfonic acid membrane branched group strengthens, thereby improves the thermal stability and the acid acceptance energy of composite membrane.
4, the composite membrane that the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and existing original position composite methods are prepared carries out acid acceptance and can test.Testing method is as follows: film to be measured is weighed behind the dry 16h in 100 ℃ of loft drier, be designated as W
1, immerse 80 ℃ of heating in water bath 5h in the 0.5M aqueous sulfuric acid, deionized water drip washing, dry 16h in 100 ℃ of loft drier weighs again, is designated as W
2Then the massfraction that loses in sulphuric acid soln of film is [100 (W
2-W
1)/W
2] %.The inorganics doped perfluorinated sulfonic acid composite membrane rate of weight loss that tests out existing original position composite methods preparation is 3.5%～4.0%, and the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance rate of weight loss of present embodiment preparation only is 0.1%, illustrates that the acid acceptance of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment is good.
5, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the test of specific conductivity, test result is that the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance specific conductivity of present embodiment preparation under 100% the condition is 0.08Scm at 90 ℃, relative humidity as shown in Figure 3 as can be seen from Figure 3
-1, apparently higher than the specific conductivity of the composite membrane of prior art for preparing.
6, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the calculating of overall target, the overall target of film is represented with following formula usually:
β represents overall target in the formula, and σ is the proton conductivity of dielectric film, and P is the methanol permeability of dielectric film, and the β value is big more, and the selectivity of expression film is good more.The overall target of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation is 5.5, the composite membrane of existing original position composite methods preparation is 0.3～0.5, illustrates that the overall target of the composite membrane of present embodiment preparation obviously is better than the overall target of the composite membrane of prior art for preparing.
Embodiment 20: present embodiment prepares the method for the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance and carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, and putting into concentration again is the Ca (NO of 1mol/L
3)
2Flood 30min～120min in the mixed solution of solution and methyl alcohol, wherein Ca (NO
3)
2Solution and methyl alcohol are according to the mixed of volume ratio 1:1～5, taking out the back cleans 3～5 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, dry 2h under 100 ℃ condition then, composite membrane is placed the stainless steel autoclave of teflon lined, adding concentration is the (NH of 1mol/L again
4)
2HPO
4Solution, pH value to 8～12 of regulator solution, the baking oven of putting into 120 ℃～180 ℃ heated 1～10 day; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
That present embodiment prepares is nanometer Ca
5(PO
4)
3The adulterated perfluorinated sulfonic acid composite membrane of OH.
In the step 2 of present embodiment composite membrane is placed the stainless steel autoclave back of teflon lined to add (NH
4)
2HPO
4Solution, (NH
4)
2HPO
4The add-on of solution is not as the criterion can there not to be composite membrane.
Embodiment 21: the difference of present embodiment and embodiment 20 is: in the step 1 perfluoro sulfonic acid membrane put into mass concentration and be 4% hydrogen peroxide solution and soak.Other step and parameter are identical with embodiment 20.
Embodiment 22: the difference of present embodiment and embodiment 20 is: the perfluoro sulfonic acid membrane of in the step 1 hydrogen peroxide dipping being crossed deionized water rinsing 4 times.Other step and parameter are identical with embodiment 20.
Embodiment 23: the difference of present embodiment and embodiment 20 is: the perfluoro sulfonic acid membrane that in the step 1 sulfuric acid was soaked deionized water rinsing 4 times.Other step and parameter are identical with embodiment 20.
Embodiment 24: the difference of present embodiment and embodiment 20 is: putting into concentration in the step 2 is the Ca (NO of 1mol/L
3)
2With flood 60min～90min in the mixed solution of methyl alcohol, Ca (NO wherein
3)
2Solution and methyl alcohol are according to the mixed of volume ratio 1:2～4.Other step and parameter are identical with embodiment 20.
Embodiment 25: the difference of present embodiment and embodiment 20 is: putting into concentration in the step 2 is the Ca (NO of 1mol/L
3)
2With flood 75min in the mixed solution of methyl alcohol, Ca (NO wherein
3)
2Solution and methyl alcohol are according to the mixed of volume ratio 1:3.Other step and parameter are identical with embodiment 20.
Embodiment 26: the difference of present embodiment and embodiment 20 is: in the step 2 from Ca (NO
3)
2Taking out the back in the mixed solution of solution and methyl alcohol cleans 4 times with dehydrated alcohol.Other step and parameter are identical with embodiment 20.
Embodiment 27: the difference of present embodiment and embodiment 20 is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, adding 50mL～110mL, concentration are the NH of 1mol/L
4)
2HPO
4Solution, pH value to 9～11 of regulator solution.Other step and parameter are identical with embodiment 20.
Embodiment 28: the difference of present embodiment and embodiment 20 is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, adding 80mL, concentration are the (NH of 1mol/L
4)
2HPO
4Solution, the pH value to 10 of regulator solution.Other step and parameter are identical with embodiment 20.
Embodiment 29: the difference of present embodiment and embodiment 20 is: the baking oven of putting into 130 ℃～170 ℃ in the step 2 heated 3～8 days.Other step and parameter are identical with embodiment 20.
Embodiment 30: the difference of present embodiment and embodiment 20 is: the baking oven of putting into 140 ℃～160 ℃ in the step 2 heated 4～7 days.Other step and parameter are identical with embodiment 20.
The embodiment hentriaconta-: the difference of present embodiment and embodiment 20 is: the baking oven of putting into 150 ℃ in the step 2 heated 5 days.Other step and parameter are identical with embodiment 20.
Embodiment 33: present embodiment prepares the method for the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance and carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 4% the hydrogen peroxide solution, take out back deionized water rinsing 4 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 4 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 4 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, and putting into concentration again is the Ca (NO of 1mol/L
3)
2Flood 30min～120min in the mixed solution of solution and methyl alcohol, wherein Ca (NO
3)
2Solution and methyl alcohol are according to the mixed of volume ratio 1:3, taking out the back cleans 4 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, dry 2h under 100 ℃ condition then, composite membrane is placed the stainless steel autoclave of teflon lined, adding 80mL, concentration are the (NH of 1mol/L again
4)
2HPO
4Solution, the pH value to 10 of regulator solution, the baking oven of putting into 150 ℃ heated 6 days; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
That present embodiment prepares is nanometer Ca
5(PO
4)
3The adulterated perfluorinated sulfonic acid composite membrane of OH.
Nanometer Ca with the present embodiment preparation
5(PO
4)
3The adulterated perfluorinated sulfonic acid composite membrane of OH carries out test performance, need before the performance test film of preparing is carried out cleaning pretreatment: with composite membrane deionized water drip washing 5 times of present embodiment preparation, the sulphuric acid soln of putting into 80 ℃, concentration then and be 0.1mol/L heats 30min, use deionized water rinsing once more 5 times, 80 ℃ of heating in water bath and washing three times in deionized water at last, each half an hour, after handling totally, film carries out following performance test:
1, the initial heat decomposition temperature of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that present embodiment is prepared is 357 ℃, and what adopt existing original position composite methods preparation is 330 ℃, and the Heat stability is good of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that the method for present embodiment is prepared is described.
2, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the test of water content, test condition is as follows: the water content difference of composite membrane calculates in the of poor quality of hygrometric state and dry state according to film, above-mentioned composite membrane is flooded 12h respectively in 25 ℃ of deionized waters, blot the water on film surface with filter paper, its weight in wet base of weighing W
WetThen with film its dry weight of weighing W behind 110 ℃ of baking 16h
DryThe massfraction of water is [100 (W in the film
Wet-W
Dry)/W
Wet] %.Testing out present embodiment, to prepare the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance water content be 210%, existing method be 35%, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that the present embodiment preparation is described has the ability of higher maintenance water, thereby guarantees that composite membrane has proton conductivity preferably.
3, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out XRD and examination of infrared spectrum, the XRD test result as shown in Figure 4, the examination of infrared spectrum result as shown in Figure 5, as can be seen from Figure 4 and Figure 5, the adulterated inorganics of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation is crystal form, and the interaction of crystallization phases inorganics and perfluoro sulfonic acid membrane branched group strengthens, thereby improves the thermal stability and the acid acceptance energy of composite membrane.
4, the composite membrane that the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and existing original position composite methods are prepared carries out acid acceptance and can test, and testing method is as follows: film to be measured is weighed behind the dry 16h in 100 ℃ of loft drier, be designated as W
1, immerse 80 ℃ of heating in water bath 5h in the 0.5M aqueous sulfuric acid, deionized water drip washing, dry 16h in 100 ℃ of loft drier weighs again, is designated as W
2Then the massfraction that loses in sulphuric acid soln of film is [100 (W
2-W
1)/W
2] %.The inorganics doped perfluorinated sulfonic acid composite membrane rate of weight loss that tests out existing original position composite methods preparation is 1.3%～1.5%, and the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance rate of weight loss of present embodiment preparation (does not have weightlessness for-0.9%, weight increases), illustrate that the acid acceptance of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment is good.
5, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the test of specific conductivity, test result is that the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance specific conductivity of present embodiment preparation under 100% the condition is 0.14Scm at 90 ℃, relative humidity as shown in Figure 6 as can be seen from Figure 6
-1, apparently higher than the specific conductivity of the composite membrane of prior art for preparing.
6, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the calculating of overall target, the overall target of film is represented with following formula usually:
β represents overall target in the formula, and σ is the proton conductivity of dielectric film, and P is the methanol permeability of dielectric film, and the β value is big more, and the selectivity of expression film is good more.The overall target of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation is 12, the composite membrane of existing original position composite methods preparation is 0.3～0.5, illustrates that the overall target of the composite membrane of present embodiment preparation obviously is better than the overall target of the composite membrane of prior art for preparing.
Embodiment 33: present embodiment prepares the method for the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance and carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, puts into the TiCl that concentration is 1mol/L again
4Flood 30min～120min in the mixed solution of solution and methyl alcohol, wherein TiCl
4Solution and methyl alcohol are according to the mixed of volume ratio 1:1～5, put into volumetric concentration then and be 16%～50% ammoniacal liquor and flood 3h, taking out the back cleans 3～5 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, composite membrane is placed the stainless steel autoclave of teflon lined, adding concentration is the Ba (OH) of 1mol/L again
2Solution, pH value to 8～14 of regulator solution, the baking oven of putting into 120 ℃～180 ℃ heated 1～10 day; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
That present embodiment prepares is nanometer BaTiO
3Adulterated perfluorinated sulfonic acid composite membrane.
In the step 2 of present embodiment composite membrane is placed the stainless steel autoclave back of teflon lined to add Ba (OH)
2Solution, Ba (OH)
2The add-on of solution is not as the criterion can there not to be composite membrane.
Embodiment 34: the difference of present embodiment and embodiment 33 is: in the step 1 perfluoro sulfonic acid membrane put into mass concentration and be 4% hydrogen peroxide solution and soak.Other step and parameter are identical with embodiment 33.
Embodiment 35: the difference of present embodiment and embodiment 33 is: the perfluoro sulfonic acid membrane of in the step 1 hydrogen peroxide dipping being crossed deionized water rinsing 4 times.Other step and parameter are identical with embodiment 33.
Embodiment 36: the difference of present embodiment and embodiment 33 is: the perfluoro sulfonic acid membrane that in the step 1 sulfuric acid was soaked deionized water rinsing 4 times.Other step and parameter are identical with embodiment 33.
Embodiment 37: the difference of present embodiment and embodiment 33 is: put into the TiCl that concentration is 1mol/L in the step 2
4Flood 60min～90min in the mixed solution of solution and methyl alcohol, wherein TiCl
4Solution and methyl alcohol are according to the mixed of volume ratio 1:2～4.Other step and parameter are identical with embodiment 33.
Embodiment 38: the difference of present embodiment and embodiment 33 is: put into the TiCl that concentration is 1mol/L in the step 2
4Flood 75min in the mixed solution of solution and methyl alcohol, wherein TiCl
4Solution and methyl alcohol are according to the mixed of volume ratio 1:3.Other step and parameter are identical with embodiment 33.
Embodiment 39: the difference of present embodiment and embodiment 33 is: put into volumetric concentration in the step 2 and be 24%～42% ammoniacal liquor and flood.Other step and parameter are identical with embodiment 33.
Embodiment 40: the difference of present embodiment and embodiment 33 is: put into volumetric concentration in the step 2 and be 32%～34% ammoniacal liquor and flood.Other step and parameter are identical with embodiment 33.
Embodiment 41: the difference of present embodiment and embodiment 33 is: put into volumetric concentration in the step 2 and be 33% ammoniacal liquor and flood.Other step and parameter are identical with embodiment 33.
Embodiment 42: the difference of present embodiment and embodiment 33 is: take out the back in the step 2 and clean 4 times with dehydrated alcohol from ammoniacal liquor.Other step and parameter are identical with embodiment 33.
Embodiment 43: the difference of present embodiment and embodiment 33 is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, adding 60mL～100mL, concentration are the Ba (OH) of 1mol/L
2Solution, pH value to 10～12 of regulator solution.Other step and parameter are identical with embodiment 33.
Embodiment 44: the difference of present embodiment and embodiment 33 is: in the step 2 composite membrane is placed the stainless steel autoclave of teflon lined, adding 80mL, concentration are the Ba (OH) of 1mol/L
2Solution, the pH value to 11 of regulator solution.Other step and parameter are identical with embodiment 33.
Embodiment 45: the difference of present embodiment and embodiment 33 is: the baking oven of putting into 130 ℃～170 ℃ in the step 2 heated 3～8 days.Other step and parameter are identical with embodiment 33.
Embodiment 46: the difference of present embodiment and embodiment 33 is: the baking oven of putting into 140 ℃～160 ℃ in the step 2 heated 4～7 days.Other step and parameter are identical with embodiment 33.
Embodiment 47: the difference of present embodiment and embodiment 33 is: the baking oven of putting into 150 ℃ in the step 2 heated 5 days.Other step and parameter are identical with embodiment 33.
Embodiment 48: present embodiment prepares the method for the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance and carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 4% the hydrogen peroxide solution, take out back deionized water rinsing 4 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 4 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 4 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, puts into the TiCl that concentration is 1mol/L again
4Flood 70min in the mixed solution of solution and methyl alcohol, wherein TiCl
4Solution and methyl alcohol are according to the mixed of volume ratio 1:3, put into volumetric concentration then and be 35% ammoniacal liquor and flood 3h, taking out the back cleans 4 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, composite membrane is placed the stainless steel autoclave of teflon lined, adding 60mL, concentration are the Ba (OH) of 1mol/L again
2Solution, the pH value to 10 of regulator solution, the baking oven of putting into 150 ℃ heated 6 days; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
That present embodiment prepares is nanometer BaTiO
3Adulterated perfluorinated sulfonic acid composite membrane.
Nanometer BaTiO with the present embodiment preparation
3Adulterated perfluorinated sulfonic acid composite membrane carries out test performance, need before the performance test film of preparing is carried out cleaning pretreatment: with composite membrane deionized water drip washing 5 times of present embodiment preparation, the sulphuric acid soln of putting into 80 ℃, concentration then and be 0.1mol/L heats 30min, use deionized water rinsing once more 5 times, 80 ℃ of heating in water bath and washing three times in deionized water at last, each half an hour, after handling totally, film carries out following performance test:
1, the initial heat decomposition temperature of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that present embodiment is prepared is 345 ℃, and what adopt existing original position composite methods preparation is 330 ℃, and the Heat stability is good of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that the method for present embodiment is prepared is described.
2, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the test of water content, test condition is as follows: the water content difference of composite membrane calculates in the of poor quality of hygrometric state and dry state according to film, above-mentioned composite membrane is flooded 12h respectively in 25 ℃ of deionized waters, blot the water on film surface with filter paper, its weight in wet base of weighing W
WetThen with film its dry weight of weighing W behind 110 ℃ of baking 16h
DryThe massfraction of water is [100 (W in the film
Wet-W
Dry)/W
Wet] %.Testing out present embodiment, to prepare the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance water content be 86%, existing method be 38%, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance that the present embodiment preparation is described has the ability of higher maintenance water, thereby guarantees that composite membrane has proton conductivity preferably.
3, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out XRD and examination of infrared spectrum, the XRD test result as shown in Figure 7, the examination of infrared spectrum result as shown in Figure 8, as can be seen from Figures 7 and 8, the adulterated inorganics of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation is crystal form, and the interaction of crystallization phases inorganics and perfluoro sulfonic acid membrane branched group strengthens, thereby improves the thermal stability and the acid acceptance energy of composite membrane.
4, the composite membrane that the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and existing original position composite methods are prepared carries out acid acceptance and can test, and testing method is as follows: film to be measured is weighed behind the dry 16h in 100 ℃ of loft drier, be designated as W
1, immerse 80 ℃ of heating in water bath 5h in the 0.5M aqueous sulfuric acid, deionized water drip washing, dry 16h in 100 ℃ of loft drier weighs again, is designated as W
2Then the massfraction that loses in sulphuric acid soln of film is [100 (W
2-W
1)/W
2] %.The inorganics doped perfluorinated sulfonic acid composite membrane rate of weight loss that tests out existing original position composite methods preparation is 0.8%～1.0%, and the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance rate of weight loss of present embodiment preparation (does not have weightlessness for-0.7%, weight increases), illustrate that the acid acceptance of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment is good.
5, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the test of specific conductivity, test result is that the adulterated perfluorinated sulfonic acid composite membrane of the nano-inorganic substance specific conductivity of present embodiment preparation under 100% the condition is 0.11Scm at 90 ℃, relative humidity as shown in Figure 9 as can be seen from Figure 9
-1, apparently higher than the specific conductivity of the composite membrane of prior art for preparing.
6, the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation and the composite membrane of existing original position composite methods preparation are carried out the calculating of overall target, the overall target of film is represented with following formula usually:
β represents overall target in the formula, and σ is the proton conductivity of dielectric film, and P is the methanol permeability of dielectric film, and the β value is big more, and the selectivity of expression film is good more.The overall target of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance of present embodiment preparation is 8, the composite membrane of existing original position composite methods preparation is 0.3～0.4, illustrates that the overall target of the composite membrane of present embodiment preparation obviously is better than the overall target of the composite membrane of prior art for preparing.
Claims (10)
1, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance, it is characterized in that the method for preparing the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, the dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, put into the metal-nitrate solutions that concentration is 1mol/L and the mixed solution of methyl alcohol again and flood 30min～120min, wherein metal-nitrate solutions and methyl alcohol are according to the mixed of volume ratio 1:1～5, put into volumetric concentration then and be 16%～50% ammoniacal liquor and flood 3h, taking out the back cleans 3～5 times with dehydrated alcohol, then at 80 ℃ of dry 16h, again composite membrane is placed the stainless steel autoclave of teflon lined, add deionized water, the baking oven of putting into 120 ℃～180 ℃ heated 1～24 hour; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance; Wherein the solute of the metal-nitrate solutions in the step 2 is Mg (NO
3)
2, Al (NO
3)
3, Ga (NO
3)
3, In (NO
3)
3, La (NO
3)
3, Y (NO
3)
3Or Ce (NO
3)
3
2, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance according to claim 1 is characterized in that in the step 1 perfluoro sulfonic acid membrane put into mass concentration and is 4% hydrogen peroxide solution and soaks.
3, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance according to claim 1 is characterized in that putting in the step 2 metal-nitrate solutions that concentration is 1mol/L and methyl alcohol and floods 50min～100min according to the mixed solution of the mixed of volume ratio 1:2～4.
4, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance according to claim 1 is characterized in that putting in the step 2 volumetric concentration and is 25%～40% ammoniacal liquor and floods.
5, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance according to claim 1 is characterized in that in the step 2 composite membrane being placed the stainless steel autoclave of teflon lined, adds 60mL～100mL deionized water.
6, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance according to claim 1, the baking oven that it is characterized in that putting in the step 2 140 ℃～160 ℃ heated 7～18 hours.
7, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance, it is characterized in that the method for preparing the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, and putting into concentration again is the Ca (NO of 1mol/L
3)
2Flood 30min～120min in the mixed solution of solution and methyl alcohol, wherein Ca (NO
3)
2Solution and methyl alcohol are according to the mixed of volume ratio 1:1～5, taking out the back cleans 3～5 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, dry 2h under 100 ℃ condition then, composite membrane is placed the stainless steel autoclave of teflon lined, adding concentration is the (NH of 1mol/L again
4)
2HPO
4Solution, pH value to 8～12 of regulator solution, the baking oven of putting into 120 ℃～180 ℃ heated 1～10 day; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
8, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance according to claim 7 is characterized in that in the step 2 composite membrane being placed the stainless steel autoclave of teflon lined, adds 80mL, concentration is the (NH of 1mol/L
4)
2HPO
4Solution, the pH value to 10 of regulator solution.
9, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance, it is characterized in that the method for preparing the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance carries out according to following steps: one, the pre-treatment of perfluoro sulfonic acid membrane: perfluoro sulfonic acid membrane is put into 80 ℃, mass concentration is to soak 1h in 3%～5% the hydrogen peroxide solution, take out back deionized water rinsing 3～5 times, put into 80 ℃ again, concentration is to soak 1h in the sulphuric acid soln of 0.5mol/L, with deionized water rinsing 3～5 times, in 80 ℃ deionized water, soak 3 times then, the each immersion half an hour, use deionized water rinsing afterwards 3～5 times, promptly obtain handling clean perfluoro sulfonic acid membrane; Two, dopen Nano inorganics: the mixed solution that the clean perfluoro sulfonic acid membrane that step 1 is obtained is put into the first alcohol and water floods 5min, and wherein the first alcohol and water is the mixed of 2:1 according to volume ratio, puts into the TiCl that concentration is 1mol/L again
4Flood 30min～120min in the mixed solution of solution and methyl alcohol, wherein TiCl
4Solution and methyl alcohol are according to the mixed of volume ratio 1:1～5, put into volumetric concentration then and be 16%～50% ammoniacal liquor and flood 3h, taking out the back cleans 3～5 times with dehydrated alcohol, dry 16h under 80 ℃ condition again, composite membrane is placed the stainless steel autoclave of teflon lined, adding concentration is the Ba (OH) of 1mol/L again
2Solution, pH value to 8～14 of regulator solution, the baking oven of putting into 120 ℃～180 ℃ heated 1～10 day; Promptly obtain the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance.
10, the preparation method of the adulterated perfluorinated sulfonic acid composite membrane of nano-inorganic substance according to claim 9 is characterized in that putting in the step 2 TiCl that concentration is 1mol/L
4Flood 75min in the mixed solution of solution and methyl alcohol, TiCl
4Solution and methyl alcohol are according to the mixed of volume ratio 1:3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101369287A CN101376717A (en) | 2008-08-15 | 2008-08-15 | Preparation of nano inorganic doped perfluorosulfonated compound film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101369287A CN101376717A (en) | 2008-08-15 | 2008-08-15 | Preparation of nano inorganic doped perfluorosulfonated compound film |
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|---|---|
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ID=40420459
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733010B (en) * | 2009-12-10 | 2011-01-26 | 山东东岳神舟新材料有限公司 | Doped double cross-linking reinforced perfluorinated proton exchange membrane and preparation method thereof |
| CN102260399A (en) * | 2011-06-07 | 2011-11-30 | 上海三爱富新材料股份有限公司 | Method for producing perfluorosulfonic acid proton exchange film |
-
2008
- 2008-08-15 CN CNA2008101369287A patent/CN101376717A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733010B (en) * | 2009-12-10 | 2011-01-26 | 山东东岳神舟新材料有限公司 | Doped double cross-linking reinforced perfluorinated proton exchange membrane and preparation method thereof |
| CN102260399A (en) * | 2011-06-07 | 2011-11-30 | 上海三爱富新材料股份有限公司 | Method for producing perfluorosulfonic acid proton exchange film |
| CN102260399B (en) * | 2011-06-07 | 2013-11-20 | 上海三爱富新材料股份有限公司 | Method for producing perfluorosulfonic acid proton exchange film |
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