CN103319741A - preparation method of sulfonated polyimide/titanium dioxide composite proton conductive membrane - Google Patents
preparation method of sulfonated polyimide/titanium dioxide composite proton conductive membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of sulfonated polyimide/titanium dioxide composite proton conductive membrane, characterized in that under the protection of nitrogen, 2,2'-disulfonic acid benzidine, meta-cresol and triethylamine are put into a reactor; then 1,4,5,8-naphthalene tetracarboxylic dianhydride, benzoic acid and 4,4' oxydianiline are added, stirred and heated to 70-100 DEG C for reaction for 2-4 hours; then heated to 180-200 DEG C for reaction for 10-20 hours; and then the mixture is cooled and poured into acetone for filtering; the solids are washed by acetone and then dried to obtain sulfonated polyimide of triethylamine salt type. The sulfonated polyimide of triethylamine salt type is dissolved in an organic solvent, and mixed with an organic solvent dispersion liquid of titanium dioxide powder, then casted for filming, and then dried, immersed and washed to obtain sulfonated polyimide proton /titanium dioxide composite proton conductive membrane; the conductive membrane is suitable for an all-vanadium redox flow battery and a fuel cell with good performance.
Description
Technical field
The invention belongs to the preparation method of battery diaphragm, relate to the preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film.The sulfonated polyimide that the present invention makes/titanium dioxide composite proton conducting film can be applicable in the fields such as vanadium redox battery, hydrogen-oxygen fuel cell, direct methanol fuel cell.
Background technology
Vanadium redox battery (Vanadium Redox Flow Battery, be called for short: VRB) be to equal a kind of novel green secondary cell of proposing in 1985 by Skyllas-Kazacos, have the advantages such as the harmless deep discharge of adjustable, the large electric current of capacity and power, long service life, easy to operate and maintenance.It by the large-scale accumulator system that single metal ion (vanadium ion) consists of, has avoided the electrolytic solution cross-contamination issue of other flow batteries such as Fe/Cr battery, Na/S battery etc. as a kind of positive and negative electrode redox couple.Usually, VRB can be applicable to the aspects such as peaking power source system, extensive photo-translating system, wind energy utilization system, electric car power supply.
Proton conductive membrane is one of core component of VRB, and desirable proton conductive membrane should have the advantages such as proton conductivity is high, electrochemical stability good, price is low.At present, the perfluorinated sulfonic acid Nafion series membranes that chemical stability is good, proton conductivity is high has obtained general utilization in VRB.But the price of perfluorinated sulfonic acid Nafion series membranes costliness and the vanadium of can not ignore infiltration, water migration have limited its large-scale commercial applications.Therefore, in order to reduce cost, to reduce the vanadium infiltration, improve as far as possible the comprehensive cost performance of battery, the investigator has carried out a large amount of significant trial work.In the prior art, have bibliographical information (Wang Nanfang, Peng Sui is etc. solid-state electrochemistry magazine, 2012,16,1577-1584.) utilize hydrothermal method to prepare the Nafion/TiO2 hybrid films, thereby reduce the vanadium infiltration of barrier film, the self-discharge rate of VRB is significantly reduced, improved the enclosed pasture efficient of battery; But this modification based on the Nafion film can not be from reducing the price of barrier film in essence, and therefore, in recent years, the investigator is devoted to seek the non-fluorine polymer proton conductive membrane of Cheap highly effective, thoroughly to break the VRB barrier film to the dependence of Nafion film.(anticipatory remark is expensive for document, Zhang Shouhai, Deng. chemical journal, 2011,69(21): 2583-2588.) propose to replace the Nafion film with the quaternized Phthalazinone PEKK of the non-fluorine macromolecular material anion-exchange membrane of excellent property, when being applied to VRB, the enclosed pasture efficient of battery surpasses Nafion.
Sulfonated polyimide (Sulfonated Polyimide, be called for short SPI) has that thermostability is high, physical strength large, good chemical stability.Document (Yue Mingzhu, Zhang Yaping, Wang Lei. solid state ionics, 2012,217:6-12. high mountain jewel, Zhang Yaping, Wang Lei. use the polymer science magazine, 2013,127:4150-4159.) reported a series of sulfonated polyimide proton conductive membranes based on six-ring, they all have good proton conductivity of phosphoric acid and resistance vanadium effect.But similar with the single non-fluorine polymer proton conductive membrane of the overwhelming majority, the resistance of oxidation of barrier film is poor, easily by V5+ solution oxide in the battery, cause film to produce microdefect, positive and negative electrode liquid is mixed cause that cell container descends, and then greatly affect the Long Service Life of battery.
Summary of the invention
Purpose of the present invention is intended to overcome deficiency of the prior art, by blending technology, provides a kind of organic and inorganic composite proton conducting film, i.e. the preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film.The sulfonated polyimide that the present invention makes/titanium dioxide composite proton conducting film can effectively remedy the Stable Defects that causes owing to the single film of sulfonated polyimide, and can permeate by the establishment vanadium ion, in fields such as VRB good application prospect is arranged.
For achieving the above object, the present invention adopts Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, 2,2'-disulfonic acid p-diaminodiphenyl, 4,4'-diaminodiphenyl oxide etc. is raw material, and in the meta-cresol medium, polycondensation prepares the sulfonated polyimide of triethylamine salt type under triethylamine and phenylformic acid existence and nitrogen protection; Adopt the method for blend, titanium dioxide or the butyl (tetra) titanate of different mass be distributed in the solvent, then with the sulfonated polyimide solution blending of triethylamine salt type to evenly, casting film-forming; Use again vitriolization, thereby make sulfonated polyimide/titanium dioxide composite film.
Content of the present invention is: the preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film is characterized in that comprising the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (being called for short NTDA) 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl (being called for short BDSA) 0.4～1.6 mmol, 4, the ratio of 4' diaminodiphenyl oxide (being called for short ODA) 0.4～1.6 mmol, catalyzer phenylformic acid 2.4～4.0 mmol, releasing agent triethylamine 0.8～6.4 mmol, solvent meta-cresol 90～185 mmol is got each feed composition;
B, at nitrogen (N
2) protection down, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 70～100 ℃, under this temperature, reacted 2～4 hours, be warming up to again 180～200 ℃ the reaction 10～20 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 2～3 times, then under 60～100 ℃ of temperature dry 10～30 hours, namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 5～20:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent, being mixed with mass percent concentration is the solution I of 5～15 %, be that the titania powder of 5～30nm is distributed in the organic solvent with particle diameter, be mixed with mass percent and be 3%～20% dispersion soln II, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 15～28:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, again will be with the sheet glass of film after under 60～120 ℃ of temperature dry 15～36 hours, film is stripped down from sheet glass, place again the aqueous sulfuric acid of 1.0～2.5 mol/L to soak 10～36 hours, film is taken out, with deionized water wash 2～4 times extremely neutral (that is: pH is 6～7), namely make sulfonated polyimide proton/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by;
Described organic solvent is meta-cresol (being called for short m-cresol), N, the mixture of one or more in dinethylformamide (being called for short NMF), N,N-dimethylacetamide (being called for short NMAc), methyl-sulphoxide (being called for short DMSO), the N-methyl-N-pyrrolidone (being called for short NMP).
In the content of the present invention: acetone described in the step b can replace with methyl alcohol or ethanol.
In the content of the present invention: titania powder described in the step c can replace with butyl (tetra) titanate.
In the content of the present invention: deionized water described in the step c can replace with distilled water.
In the content of the present invention: the thickness range of the sulfonated polyimide that makes described in the step c/titanium dioxide composite proton conducting film can be 10～200 μ m.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) reaction mechanism of the present invention is shown in following chemical equation:
In the formula: m, n represent the number of repeat unit in the polymkeric substance.
(2) adopt sulfonated polyimide/titanium dioxide composite film that the present invention makes since within it section be compounded with titanium dioxide, oxidation-resistance that can the Effective Raise barrier film can so that membrane structure is tightr, further improve the resistance vanadium ion performance of barrier film; Concrete experimental result is as follows: the vanadium ion permeation constant of sulfonated polyimide/titanium dioxide composite film is 1.15-7.85 * 10
-7Cm
2Min
-1, than Nafion117 film vanadium ion permeation constant 15.41 * 10
-7Cm
2Min
-1Low, can predict thus that it is applied to VRB enclosed pasture efficient and open circuit voltage is excellent than Nafion117; The composite membrane proton conductivity of sulfonated polyimide/titanium dioxide is 3.15-8.24 * 10
-2Scm
-1, its value approaches even is higher than the proton conductivity (6.41 * 10 of Nafion117 film
-2Scm
-1), this shows that this film has good proton selectivity; In addition, and shown by the sulphuric acid soln test result of the strong pentavalent vanadium ion of oxidisability, its stability has a clear superiority in than the sulfonated polyimide proton conductive membrane, will have a good application prospect in fields such as VRB;
(3) adopt the present invention, titanium dioxide has nontoxic, superior chemistry, thermally-stabilised and become easy film, and inexpensive, cost is low; Sulfonated polyimide/the titanium dioxide composite film for preparing not only had satisfactory stability but also can the establishment vanadium ion see through, keep simultaneously rational proton conductivity;
(4) preparation technology of the present invention is simple, easily operation, and cost is low, and the prepared sulfonated polyimide of the present invention/titanium dioxide composite proton conducting film has good application prospect in vanadium redox battery and fuel cell, practical.
Embodiment
Embodiment given below intends so that the invention will be further described; but can not be interpreted as it is limiting the scope of the invention; the person skilled in art to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
Embodiment 1:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film:
Under the N2 protection; in the 100mL there-necked flask, add 1.0 mmol BDSA, 10 mL meta-cresols, 2.0 mmol triethylamines; constantly being stirred to BDSA under the room temperature dissolves fully; add 2.0 mmol NTDA, 0.49 g phenylformic acid and 1.0 mmol ODA, continue stirred for several minute after; system temperature is risen to 80 ℃ of reactions 4 hours; be warming up to 180 ℃ of reactions 20 hours, stopped heating obtains sticky shaped polymer solution again.Treat that temperature is down to below 80 ℃, add 5 mL meta-cresol dilute reaction solutions, continue stirred for several minute after, pour acetone into, obtain cotton-shaped polymer precipitation, filter, solids with acetone repetitive scrubbing precipitation repeatedly to remove remaining solvent and unreacted reactant, then in 80 ℃ of dryings 20 hours;
The sulfonated polyimide of resulting triethylamine salt type is dissolved in the organic solvent meta-cresol, and to be mixed with mass percent concentration be 6% m-cresol solution I, the preparation mass percent is the meta-cresol dispersion soln II of 7% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, in 60 ℃ of dryings 24 hours, being immersed in the 1.0 mol/L aqueous sulfuric acids 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, sulfuric acid to the solution of removing remained on surface is neutral), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Control the thickness range of prepared sulfonated polyimide/titanium dioxide composite proton conducting film at 10～200 μ m.
Above-mentioned organic solvent can be replaced with by meta-cresol: DMF, N,N-dimethylacetamide, methyl-sulphoxide or N-methyl-N-pyrrolidone; Precipitation agent can replace to methyl alcohol or ethanol by acetone.
Embodiment 2:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film:
Under the N2 protection; in the 100mL there-necked flask, add 1.2 mmol BDSA, 10 mL meta-cresols, 2.4 mmol triethylamines; constantly being stirred to BDSA under the room temperature dissolves fully; add 2.0 mmol NTDA, 0.49 g phenylformic acid and 0.8 mmol ODA, continue stirred for several minute after; system temperature is risen to 80 ℃ of reactions 4 hours; be warming up to 180 ℃ of reactions 20 hours, stopped heating obtains sticky shaped polymer solution again.Treat that temperature is down to below 80 ℃, add 5 mL meta-cresol dilute reaction solutions, continue stirred for several minute after, pour acetone into, obtain cotton-shaped polymer precipitation, filter, solids with acetone repetitive scrubbing precipitation repeatedly to remove remaining solvent and unreacted reactant, then in 80 ℃ of dryings 20 hours;
The sulfonated polyimide of resulting triethylamine salt type is dissolved in the organic solvent meta-cresol, and to be mixed with mass percent concentration be 8% m-cresol solution I, the preparation mass percent is the meta-cresol dispersion soln II of 7% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, sulfuric acid to the solution of removing remained on surface is neutral), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Control the thickness range of prepared sulfonated polyimide/titanium dioxide composite proton conducting film at 10～200 μ m.
Above-mentioned organic solvent can be replaced with by meta-cresol: DMF, N,N-dimethylacetamide, methyl-sulphoxide or N-methyl-N-pyrrolidone.Precipitation agent can replace to methyl alcohol or ethanol by acetone.
Embodiment 3:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film:
Under the N2 protection; in the 100mL there-necked flask, add 1.0 mmol BDSA, 10 mL meta-cresols, 2.0 mmol triethylamines; constantly being stirred to BDSA under the room temperature dissolves fully; add 2.0 mmolNTDA, 0.49 g phenylformic acid and 1.0 mmol ODA, continue stirred for several minute after; system temperature is risen to 80 ℃ of reactions 4 hours; be warming up to 180 ℃ of reactions 20 hours, stopped heating obtains sticky shaped polymer solution again.Treat that temperature is down to below 80 ℃, add 5 mL meta-cresol dilute reaction solutions, continue stirred for several minute after, pour acetone into, obtain cotton-shaped polymer precipitation, filter, solids with acetone repetitive scrubbing precipitation repeatedly to remove remaining solvent and unreacted reactant, then in 80 ℃ of dryings 25 hours;
The sulfonated polyimide of resulting triethylamine salt type is dissolved in the organic solvent meta-cresol, and to be mixed with mass percent concentration be 8% m-cresol solution I, the preparation mass percent is the meta-cresol dispersion soln II of 6% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, sulfuric acid to the solution of removing remained on surface is neutral), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Control the thickness range of prepared sulfonated polyimide/titanium dioxide composite proton conducting film at 10～200 μ m.
Above-mentioned organic solvent can be replaced with by meta-cresol: DMF, N,N-dimethylacetamide, methyl-sulphoxide or N-methyl-N-pyrrolidone.Precipitation agent can replace to methyl alcohol or ethanol by acetone.
Embodiment 4:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film:
Under the N2 protection; in the 100mL there-necked flask, add 0.4 mmol BDSA, 15 mL meta-cresols, 1.0 mmol triethylamines; constantly being stirred to BDSA under the room temperature dissolves fully; add 2.0 mmol NTDA, 0.49 g phenylformic acid and 1.6 mmol ODA, continue stirred for several minute after; system temperature is risen to 80 ℃ of reactions 4 hours; be warming up to 180 ℃ of reactions 20 hours, stopped heating obtains sticky shaped polymer solution again.Treat that temperature is down to below 80 ℃, add 10 mL meta-cresol dilute reaction solutions, continue stirred for several minute after, pour acetone into, obtain cotton-shaped polymer precipitation, filter, solids with acetone repetitive scrubbing precipitation repeatedly to remove remaining solvent and unreacted reactant, then in 80 ℃ of dryings 24 hours;
The resulting sulfonated polyimide that gets the triethylamine salt type is dissolved in the organic solvent meta-cresol, and to be mixed with mass percent concentration be 15% m-cresol solution I, the preparation mass percent is the meta-cresol dispersion soln II of 7% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, sulfuric acid to the solution of removing remained on surface is neutral), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Control the thickness range of prepared sulfonated polyimide/titanium dioxide composite proton conducting film at 10～200 μ m.
Above-mentioned organic solvent can be replaced with by meta-cresol: DMF, N,N-dimethylacetamide, methyl-sulphoxide or N-methyl-N-pyrrolidone.Precipitation agent can replace to methyl alcohol or ethanol by acetone.
Embodiment 5:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film:
Under the N2 protection; in the 100mL there-necked flask, add 1.6 mmol BDSA, 10 mL meta-cresols, 3.2 mmol triethylamines; constantly being stirred to BDSA under the room temperature dissolves fully; add 2.0 mmol NTDA, 0.50 g phenylformic acid and 0.4 mmol ODA, continue stirred for several minute after; system temperature is risen to 80 ℃ of reactions 4 hours; be warming up to 180 ℃ of reactions 20 hours, stopped heating obtains sticky shaped polymer solution again.Treat that temperature is down to below 80 ℃, add 5 mL meta-cresol dilute reaction solutions, continue stirred for several minute after, pour acetone into, obtain cotton-shaped polymer precipitation, filter, solids with acetone repetitive scrubbing precipitation repeatedly to remove remaining solvent and unreacted reactant, then in 80 ℃ of dryings 20 hours;
The sulfonated polyimide of resulting triethylamine salt type is dissolved in the organic solvent meta-cresol, and to be mixed with mass percent concentration be 10% m-cresol solution I, the preparation mass percent is the meta-cresol dispersion soln II of 7% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, sulfuric acid to the solution of removing remained on surface is neutral), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Control the thickness range of prepared sulfonated polyimide/titanium dioxide composite proton conducting film at 10～200 μ m.
Above-mentioned organic solvent can be replaced with by meta-cresol: DMF, N,N-dimethylacetamide, methyl-sulphoxide or N-methyl-N-pyrrolidone.Precipitation agent can replace to methyl alcohol or ethanol by acetone.
Embodiment 6:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film:
The N2 protection is lower; in the 100mL there-necked flask, add 1.6 mmol BDSA, 10 mL meta-cresols, 3.2 mmol triethylamines; constantly being stirred to BDSA under the room temperature dissolves fully; add 2.0 mmol NTDA, 0.50 g phenylformic acid and 0.4 mmol ODA, continue stirred for several minute after; system temperature is risen to 80 ℃ of reactions 2 hours; be warming up to 180 ℃ of reactions 10 hours, stopped heating obtains sticky shaped polymer solution again.Treat that temperature is down to below 80 ℃, add 5 mL meta-cresol dilute reaction solutions, continue stirred for several minute after, pour acetone into, obtain cotton-shaped polymer precipitation, filter, solids with acetone repetitive scrubbing precipitation repeatedly to remove remaining solvent and unreacted reactant, then in 80 ℃ of dryings 20 hours;
The sulfonated polyimide of resulting triethylamine salt type is dissolved in the organic solvent meta-cresol, and to be mixed with mass percent concentration be 10% m-cresol solution I, the preparation mass percent is the meta-cresol dispersion soln II of 5% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, be neutral with sulfuric acid to the solution of removing remained on surface), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Control the thickness range of prepared sulfonated polyimide/titanium dioxide composite proton conducting film at 10～200 μ m.
Above-mentioned organic solvent can be replaced with by meta-cresol: DMF, N,N-dimethylacetamide, methyl-sulphoxide or N-methyl-N-pyrrolidone.Precipitation agent can replace to methyl alcohol or ethanol by acetone.
Embodiment 7:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film comprises the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (being called for short NTDA) 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl (being called for short BDSA) 0.4mmol, 4, the ratio of 4' diaminodiphenyl oxide (being called for short ODA) 0.4mmol, catalyzer phenylformic acid 2.4mmol, releasing agent triethylamine 0.8 mmol, solvent meta-cresol 90 mmol is got each feed composition;
B, under nitrogen (N2) protection, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 70～100 ℃, reaction is 2 hours under this temperature, be warming up to again 180～200 ℃ the reaction 10 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 2 times, and then vacuum-drying 10 hours under 60～120 ℃ of temperature namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 5:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent meta-cresol, be mixed with mass percent and be 5% solution I, the preparation mass percent is the meta-cresol dispersion soln II of 5% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, be neutral with sulfuric acid to the solution of removing remained on surface), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Control the thickness range of prepared sulfonated polyimide/titanium dioxide composite proton conducting film at 10～200 μ m.
Above-mentioned organic solvent can be replaced with by meta-cresol: DMF, N,N-dimethylacetamide, methyl-sulphoxide or N-methyl-N-pyrrolidone.Precipitation agent can replace to methyl alcohol or ethanol by acetone.
Embodiment 8:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film comprises the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (being called for short NTDA) 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl (being called for short BDSA) 1.6 mmol, 4, the ratio of 4' diaminodiphenyl oxide (being called for short ODA) 1.6 mmol, catalyzer phenylformic acid 4.0 mmol, releasing agent triethylamine 6.4 mmol, solvent meta-cresol 185 mmol is got each feed composition;
B, under nitrogen protection, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 70～100 ℃, reaction is 4 hours under this temperature, be warming up to again 180～200 ℃ the reaction 20 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 3 times, and then vacuum-drying 30 hours under 60～120 ℃ of temperature namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 20:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent meta-cresol, be mixed with mass percent concentration and be 15% solution I, the preparation mass percent is the meta-cresol dispersion soln II of 10% titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, be neutral with sulfuric acid to the solution of removing remained on surface), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Embodiment 9:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film comprises the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (being called for short NTDA) 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl (being called for short BDSA) 1.0mmol, 4, the ratio of 4' diaminodiphenyl oxide (being called for short ODA) 1.0 mmol, catalyzer phenylformic acid 3.2 mmol, releasing agent triethylamine 3.6 mmol, solvent meta-cresol 140 mmol is got each feed composition;
B, under nitrogen (N2) protection, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 70～100 ℃, reaction is 3 hours under this temperature, be warming up to again 180～200 ℃ the reaction 15 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 3 times, and then vacuum-drying 20 hours under 60～120 ℃ of temperature namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 12:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent meta-cresol, be mixed with mass percent concentration and be 10% solution I, the preparation mass percent is the meta-cresol dispersion soln II of 8% titanium dioxide, solution I and solution II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, be neutral with sulfuric acid to the solution of removing remained on surface), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by.
Embodiment 10:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film comprises the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (being called for short NTDA) 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl (being called for short BDSA) 1.1 mmol, 4, the ratio of 4' diaminodiphenyl oxide (being called for short ODA) 1.1 mmol, catalyzer phenylformic acid 1.4 mmol, releasing agent triethylamine 3.5 mmol, solvent meta-cresol 135 mmol is got each feed composition;
B, under nitrogen (N2) protection, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 85 ℃, reaction is 3 hours under this temperature, be warming up to again 190 ℃ the reaction 15 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 3 times, then under 80 ℃ of temperature dry 20 hours, namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 13:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent meta-cresol, being mixed with mass percent concentration is the solution I of 10 %, be that the titania powder of 5～30nm is distributed in the organic solvent meta-cresol with particle diameter, be mixed with mass percent and be 11% dispersion soln II, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 20:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, again will be with the sheet glass of film after under 90 ℃ of temperature dry 25 hours, film is stripped down from sheet glass, place again the aqueous sulfuric acid of 1.7 mol/L to soak 23 hours, film is taken out, with deionized water wash 2～4 times extremely neutral (that is: pH is 6～7), namely make sulfonated polyimide proton/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by;
Described organic solvent meta-cresol can replace with N, the mixture of one or more in dinethylformamide (being called for short NMF), N,N-dimethylacetamide (being called for short NMAc), methyl-sulphoxide (being called for short DMSO), the N-methyl-N-pyrrolidone (being called for short NMP).
Embodiment 11:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film comprises the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (being called for short NTDA) 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl (being called for short BDSA) 1.5 mmol, 4, the ratio of 4' diaminodiphenyl oxide (being called for short ODA) 1.5 mmol, catalyzer phenylformic acid 4.0 mmol, releasing agent triethylamine 6.4 mmol, solvent meta-cresol 185 mmol is got each feed composition;
B, under nitrogen (N2) protection, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 70～100 ℃, reaction is 4 hours under this temperature, be warming up to again 180～200 ℃ the reaction 18 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 3 times, then under 60～100 ℃ of temperature dry 30 hours, namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 20:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent meta-cresol, being mixed with mass percent concentration is the solution I of 15 %, be that the titania powder of 5～30nm is distributed in the organic solvent meta-cresol with particle diameter, be mixed with mass percent and be 20% dispersion soln II, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 28:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, again will be with the sheet glass of film after under 120 ℃ of temperature dry 15 hours, film is stripped down from sheet glass, place again the aqueous sulfuric acid of 2.5 mol/L to soak 10 hours, film is taken out, with deionized water wash 2～4 times extremely neutral (that is: pH is 6～7), namely make sulfonated polyimide proton/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by;
Described organic solvent meta-cresol can replace with N, the mixture of one or more in dinethylformamide (being called for short NMF), N,N-dimethylacetamide (being called for short NMAc), methyl-sulphoxide (being called for short DMSO), the N-methyl-N-pyrrolidone (being called for short NMP).
Embodiment 12:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film comprises the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride, 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl 0.6mmol, 4, the ratio of 4' diaminodiphenyl oxide 0.6 mmol, catalyzer phenylformic acid 2.4mmol, releasing agent triethylamine 0.9mmol, solvent meta-cresol 90mmol is got each feed composition;
B, under nitrogen protection, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 70 ℃, reaction is 4 hours under this temperature, be warming up to again 180 ℃ the reaction 20 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 3 times, then under 60～100 ℃ of temperature dry 10 hours, namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 5:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent meta-cresol, be mixed with mass percent concentration and be 5% solution I, be that the titania powder of 5～30nm is distributed in the organic solvent meta-cresol with particle diameter, be mixed with mass percent and be 3% dispersion soln II, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 15:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, again will be with the sheet glass of film after under 60 ℃ of temperature dry 36 hours, film is stripped down from sheet glass, place again the aqueous sulfuric acid of 1.1mol/L to soak 36 hours, film is taken out, with deionized water wash 2～4 times extremely neutral (that is: pH is 6～7), namely make sulfonated polyimide proton/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by;
Described organic solvent meta-cresol can replace with N, the mixture of one or more in dinethylformamide (being called for short NMF), N,N-dimethylacetamide (being called for short NMAc), methyl-sulphoxide (being called for short DMSO), the N-methyl-N-pyrrolidone (being called for short NMP).
Embodiment 13-19:
The preparation method of a kind of sulfonated polyimide/titanium dioxide composite proton conducting film comprises the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (being called for short NTDA) 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl (being called for short BDSA) 0.4～1.6 mmol, 4, the ratio of 4' diaminodiphenyl oxide (being called for short ODA) 0.4～1.6 mmol, catalyzer phenylformic acid 2.4～4.0 mmol, releasing agent triethylamine 0.8～6.4 mmol, solvent meta-cresol 90～185 mmol is got each feed composition;
The composition of each embodiment Raw component and mmol(mmole) see the following form:
B, under nitrogen (N2) protection, with 2,2'-disulfonic acid p-diaminodiphenyl (BDSA), meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (NTDA), phenylformic acid and 4,4' diaminodiphenyl oxide (ODA) stir and are heated to 70～100 ℃, under this temperature, reacted 2～4 hours, be warming up to again 180～200 ℃ the reaction 10～20 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 2～3 times, and then vacuum-drying 10～30 hours under 60～120 ℃ of temperature namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material can be arbitrary ratio among 5～20:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent, be mixed with mass percent concentration and be 5～15% solution I, titanium dioxide is dispersed in the organic solvent, be mixed with the dispersion soln II of titanium dioxide, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 21:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, respectively at 60 ℃ of dryings 15～24 hours, being immersed in the 1.0 mol/L sulphuric acid solns 24 hours makes it fully protonated again, film is taken out, (wash the film repetitive scrubbing titanium dioxide of sulfonated polyimide/titanium dioxide composite film surface off 3 times with deionized water at last, be neutral with sulfuric acid to the solution of removing remained on surface), namely make sulfonated polyimide/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by;
Described organic solvent can be meta-cresol (being called for short m-cresol), N, the mixture of one or more in dinethylformamide (being called for short NMF), N,N-dimethylacetamide (being called for short NMAc), methyl-sulphoxide (being called for short DMSO), the N-methyl-N-pyrrolidone (being called for short NMP).
In above-described embodiment 7-19: acetone described in the step b can replace with methyl alcohol or ethanol;
In above-described embodiment 7-19: titania powder described in the step c can replace with butyl (tetra) titanate;
In above-described embodiment 7-19: deionized water described in the step c can replace with distilled water;
In above-described embodiment 7-19: the thickness range of the sulfonated polyimide that makes described in the step c/titanium dioxide composite proton conducting film is 10～200 μ m.
The described sulfonated polyimide that makes of content of the present invention and above-described embodiment/titanium dioxide composite proton conducting film, adopt the antioxidative stability of the sulphuric acid soln test sulfonated polyimide/titanium dioxide composite film of pentavalent vanadium ion, the result shows: its stability obviously is better than single sulfonated polyimide proton conductive membrane under identical test condition.Adopt the four point probe AC impedence method to record sulfonated polyimide proton conductive membrane and the proton conductivity of sulfonated polyimide/titanium dioxide composite film in the complete wetting situation of room temperature, the result shows the proton conductivity 3.15-8.24 of sulfonated polyimide/titanium dioxide composite film * 10-2Scm-1, and its value approaches even be higher than the proton conductivity (6.41 * 10-2Scm-1) of Nafion 117 films.And the resistance vanadium effect of test sulfonated polyimide proton conductive membrane and sulfonated polyimide/titanium dioxide composite film, the vanadium ion permeation constant is 1.15-7.85 * 10-7 cm2min-1, low with the vanadium ion infiltration of Nafion film (15.41 * 10-7 cm2min-1) under equal test condition of du pont company, the resistance vanadium effect of the sulfonated polyimide/titanium dioxide composite film after the modification improves greatly, can the Effective Raise battery performance.This shows that sulfonated polyimide/titanium dioxide composite film of the present invention has good application prospect in fields such as VRB.
In above-described embodiment: each raw material that adopts is the commercially available prod:
In above-described embodiment: in the percentage that adopts, do not indicate especially, be quality (weight) percentage; Described quality (weight) part can all be gram or kilogram.
The not concrete same prior art of technology contents of narrating in content of the present invention and above-described embodiment.
In above-described embodiment: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The invention is not restricted to above-described embodiment, content of the present invention is described all can implement and have described good result.
Claims (6)
1. the preparation method of sulfonated polyimide/titanium dioxide composite proton conducting film is characterized in that comprising the following steps:
A, batching: by 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride 2 mmol, 2,2'-disulfonic acid p-diaminodiphenyl 0.4～1.6 mmol, 4, the ratio of 4' diaminodiphenyl oxide 0.4～1.6 mmol, catalyzer phenylformic acid 2.4～4.0 mmol, releasing agent triethylamine 0.8～6.4 mmol, solvent meta-cresol 90～185 mmol is got each feed composition;
B, under nitrogen protection, with 2,2'-disulfonic acid p-diaminodiphenyl, meta-cresol and triethylamine drop in the reactor, under room temperature, be stirred to the solids dissolving, add again Isosorbide-5-Nitrae, 5,8-naphthalenetetracarbacidic acidic dianhydride, phenylformic acid and 4,4' diaminodiphenyl oxide stir and are heated to 70～100 ℃, under this temperature, reacted 2～4 hours, be warming up to again 180～200 ℃ the reaction 10～20 hours, be cooled to below 80 ℃ after, reacting rear material is poured in the precipitation agent acetone, produced flocks, filter, solids is with washing with acetone 2～3 times, then under 60～100 ℃ of temperature dry 10～30 hours, namely makes the sulfonated polyimide of triethylamine salt type;
The volume ratio of described precipitation agent acetone and reacting rear material is 5～20:1;
C, the sulfonated polyimide of the triethylamine salt type that makes is dissolved in the organic solvent, being mixed with mass percent concentration is the solution I of 5～15 %, be that the titania powder of 5～30nm is distributed in the organic solvent with particle diameter, be mixed with mass percent and be 3%～20% dispersion soln II, solution I and dispersion soln II are mixed to the even mixed solution that becomes by the volume ratio of 15～28:1, then with mixed solution in cleaning, casting film-forming on the smooth sheet glass, again will be with the sheet glass of film after under 60～120 ℃ of temperature dry 15～36 hours, film is stripped down from sheet glass, place again the aqueous sulfuric acid of 1.0～2.5 mol/L to soak 10～36 hours, film is taken out, with deionized water wash 2～4 times to neutral, namely make sulfonated polyimide proton/titanium dioxide composite proton conducting film, be soaked in the deionized water stand-by;
Described organic solvent is one or more the mixture in meta-cresol, DMF, N,N-dimethylacetamide, methyl-sulphoxide, the N-methyl-N-pyrrolidone.
2. by the preparation method of the described sulfonated polyimide of claim 1/titanium dioxide composite proton conducting film, it is characterized in that: acetone described in the step b replaces with methyl alcohol or ethanol.
3. by the preparation method of claim 1 or 2 described sulfonated polyimide/titanium dioxide composite proton conducting films, it is characterized in that: titania powder replaces with butyl (tetra) titanate described in the step c.
4. by the preparation method of claim 1 or 2 described sulfonated polyimide/titanium dioxide composite proton conducting films, it is characterized in that: deionized water replaces with distilled water described in the step c.
5. by the preparation method of the described sulfonated polyimide of claim 3/titanium dioxide composite proton conducting film, it is characterized in that: deionized water replaces with distilled water described in the step c.
6. by the preparation method of claim 1 or 2 described sulfonated polyimide/titanium dioxide composite proton conducting films, it is characterized in that: the thickness range of the sulfonated polyimide that makes described in the step c/titanium dioxide composite proton conducting film is 10～200 μ m.
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| CN104183806A (en) * | 2014-08-13 | 2014-12-03 | 江苏安瑞达新材料有限公司 | Composite lithium battery diaphragm and preparation method thereof |
| CN105085913A (en) * | 2015-08-17 | 2015-11-25 | 西南科技大学 | Preparation method of sulfonated polyimide (SPI) proton conducting membrane containing branched structure |
| CN113731510A (en) * | 2021-09-01 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of titanium dioxide/polyimide composite material |
| CN113731376A (en) * | 2021-09-01 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of polyimide and aluminum ion complex |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104183806A (en) * | 2014-08-13 | 2014-12-03 | 江苏安瑞达新材料有限公司 | Composite lithium battery diaphragm and preparation method thereof |
| CN105085913A (en) * | 2015-08-17 | 2015-11-25 | 西南科技大学 | Preparation method of sulfonated polyimide (SPI) proton conducting membrane containing branched structure |
| CN105085913B (en) * | 2015-08-17 | 2017-12-19 | 西南科技大学 | A kind of preparation method of the sulfonated polyimide proton conductive membrane containing branched structure |
| CN113731510A (en) * | 2021-09-01 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of titanium dioxide/polyimide composite material |
| CN113731376A (en) * | 2021-09-01 | 2021-12-03 | 大同共聚(西安)科技有限公司 | Preparation method of polyimide and aluminum ion complex |
| CN113731376B (en) * | 2021-09-01 | 2023-07-25 | 大同共聚(西安)科技有限公司 | Preparation method of polyimide and aluminum ion complex |
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