CN103897335A - Modified silicon nano-tube hybrid membrane as well as preparation process and application thereof - Google Patents

Modified silicon nano-tube hybrid membrane as well as preparation process and application thereof Download PDF

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CN103897335A
CN103897335A CN201410092420.7A CN201410092420A CN103897335A CN 103897335 A CN103897335 A CN 103897335A CN 201410092420 A CN201410092420 A CN 201410092420A CN 103897335 A CN103897335 A CN 103897335A
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nano
tube
phosphoric acid
acid modification
sulfonated polyether
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姜忠义
何光伟
聂玲丽
吴洪
李宗雨
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Tianjin University
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Abstract

The invention relates to a hybrid membrane, and particularly relates to a sulfonated polyether ether ketone/poly(vinylphosphinc acid) functionalized silicon nano-tube hybrid membrane as well as a preparation process and application thereof, and belongs to the field of fuel battery proton exchange membranes. According to the preparation process, a poly(vinylphosphinc acid) functionalized nano-tube is obtained by in-situ polymerization of a silicon dioxide/aluminum oxide nano-rod as the template decorated by a carbon-carbon double bond; the nano-tube prepared and sulfonated polyether ether ketone are mixed together to obtain a casting solution which is subjected to tape casting and heat treatment to form the membrane. The hybrid membrane as well as the preparation process and application thereof have the advantages that a process for preparing inorganic/organic double-layer nanotubes is provided, the preparation is simple, and the structure is controllable. Based on the poly(vinylphosphinc acid) functionalized silicon nano-tube hybrid membrane, a fast proton transfer channel can be built in the membrane, and the proton conductivity of sulfonated polyether ether ketone is improved; moreover, the methanol diffusion resistance and mechanical strength of the membrane are enhanced; the hybrid membrane prepared according to the process can be used in proton exchange membrane fuel batteries.

Description

Modified silicon nanotube hybridized film and its preparation method and application
Technical field
The present invention relates to modified silicon nanotube hybridized film and its preparation method and application, relate in particular to a kind of sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film and its preparation method and application, belong to fuel battery proton exchange film technical field.
Background technology
Proton Exchange Membrane Fuel Cells is the representative of new forms of energy, and it is directly converted into electric energy by the chemical energy of fuel, possesses green, the advantage such as efficient and portable and is subject to broad research.Proton exchange membrane is the core component of fuel cell, and the proton conductivity of reinforced film is the key that improves battery over-all properties.Sulfonated polyether-ether-ketone because of its cost low, thermostability, mechanical property and features good methanol diffusion resistance and become one of proton exchange membrane material of greatest concern.But the low bottleneck that is restricting application that remains of the proton conductivity of this film.In film, building continuous proton transfer passage is the effective means that improves its proton conductivity.Nanotube has the continuous feature of one dimension, the proton transfer passage that nanotube self load is highdensity leads proton carrier and just can build in film high-efficiency and continuous, thereby strengthening proton conductivity.In addition, the evolving path that nanotube can bending fuel molecule in film, the resistance alcohol ability of reinforcing membrane; Nanotube can also be transferred to mechanical load self and the mechanical property of reinforcing membrane.
Summary of the invention
The object of the present invention is to provide a kind of sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film and preparation method thereof, and application in fuel cell.Described hybridized film, for Proton Exchange Membrane Fuel Cells, has better proton conductivity, higher alcohol-rejecting ability and good mechanical stability.
Sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film of the present invention is by polyvinyl phosphoric acid modification nano-tube and the preparation of polymer sulfonated polyether-ether-ketone physical blending, described polyvinyl phosphoric acid modification nano-tube is synthetic nano-tube using Nano bars of alumina as one dimension template, introduce carbon-carbon double bond with 3-(trimethoxysilyl) propyl group-2-methyl-2-acrylate in nanotube surface and think that phosphoric acid modification provides avtive spot, then as phosphoric acid modification agent, nano-tube is carried out to phosphoric acid modification with vinyl phosphoric acid dimethyl ester, finally with hydrochloric acid by Nano bars of alumina etching, and phosphoric acid ester is converted into phosphate group, form hollow polyvinyl phosphoric acid modification nano-tube.The preparation method of hybridized film comprises the following steps:
One, the preparation of polyvinyl phosphoric acid modification nano-tube
1) preparation of Nano bars of alumina.Under room temperature to AlCl 3in solution, slowly drip ammonia soln, produce white precipitate, centrifuge washing obtains aluminium hydroxide white precipitate.In white precipitate, add deionized water, add rare H of 0-0.032 M with the mass ratio of white precipitate and dilute sulphuric acid 1:5-1:20 2sO 4solution also stirs, and then mixed solution is poured in polytetrafluoroethylcontainer container, puts into retort furnace.Rise to 200 by room temperature oCrear constant temperature 24h, heat-up rate is 5 oc/min.After hydro-thermal reaction finishes, centrifuge washing reaction product to pH value of solution approaches neutral, and then lyophilize obtains Nano bars of alumina.Can control the structure and morphology of nanometer rod by adjusting the concentration of sulfuric acid, further adjust the form of nano-tube.
2) preparation of nano-tube and finishing.Take the ultrasonic 200 mL ethanol that are scattered in of Nano bars of alumina prepared by 0.15 g step 1), 12 mL water, 1.2 mL ammoniacal liquor, in 0.3 mL tetraethoxy mixing solutions, 30 ounder C, stir 24 h, introduce silicon dioxide layer on Nano bars of alumina surface, form Silica Nanotube.Add 0.2 mL 3-(trimethoxysilyl) propyl group-2-methyl-2-acrylate to continue stirring reaction 24 h, form carbon-carbon double bond on nano-tube surface, for phosphorylation reaction provides avtive spot.Centrifugal, washing after, 60 oClower vacuum-drying 24 h obtain the nano-tube that carbon-carbon double bond is modified above.
3) phosphoric acid modification of nano-tube.By 0.05 g step 2) nano-tube modified of the carbon-carbon double bond prepared is scattered in 80 mL acetonitriles, add 0.6 mL vinyl phosphoric acid dimethyl ester phosphoric acid modification agent, 0.4 mL divinyl benzene crosslinked agent, 0.02 g 2,2'-Diisopropyl azodicarboxylate reacts 80 min under boiling state, will after product separation, clean with ethanol, be distributed in the hydrochloric acid soln of 10 M, in 100 oClower back hydrolysis 24 h, are converted into phosphate group by dimethyl phosphate, and etch away Nano bars of alumina and obtain the silicon-dioxide tubulose structure of hollow, and centrifuge washing, to neutral, is finally placed in 60 oCthe above polyvinyl phosphoric acid modification nano-tube that obtains of vacuum oven 24 h.
Two, the preparation of sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film
Be scattered in nitrogen dimethylformamide solution ultrasonic polyvinyl phosphoric acid modification nano-tube, sulfonated polyether-ether-ketone is added and in nitrogen dimethylformamide solution, stirs 24 h and dissolve.Above-mentioned two kinds of solution mix and blend 2 h are obtained to film-casting liquid, and wherein the mass ratio of nanotube and sulfonated polyether-ether-ketone is 1:100-1:10.After standing and defoaming, film-casting liquid is poured on clean sheet glass to 60 othermal treatment 12 h under C, then 80 othermal treatment 12 h under C.Be cooled to after room temperature, film is taken off from sheet glass, be then placed on acidification 48 h in the sulphuric acid soln of 2 M, be washed till neutrality with deionized water and be placed on 60 oCmore than vacuum oven 24 h, obtain sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film.
Sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film prepared by aforesaid method, as Proton Exchange Membrane Fuel Cells.Polyvinyl phosphoric acid modification nano-tube can effectively strengthen proton conductivity, alcohol-rejecting ability and the physical strength of hybridized film.
The invention has the advantages that: a kind of sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film is provided, and preparation method is simple.Polyvinyl phosphoric acid modification nano-tube can build proton transfer passage fast in film, significantly increases the proton conductivity of sulfonated polyether-ether-ketone; And alcohol-rejecting ability and physical strength that can reinforcing membrane.Prepared hybridized film is expected to for Proton Exchange Membrane Fuel Cells.
Accompanying drawing explanation
Fig. 1 is the high power profile scanning electron micrograph of pure sulfonated polyether-ether-ketone film made in comparative example.
Fig. 2 is the high power profile scanning electron micrograph of hybridized film film 3 in embodiment.
Embodiment
Embodiment 1
One, the preparation of polyvinyl phosphoric acid modification nano-tube
Take 5.4 g AlCl 36H 2o is dissolved in 22.5 mL water, gets 5.2 mL ammonia solns and joins in 22.5 mL water and dilute.Under room temperature to AlCl 3in solution, slowly drip ammonia soln, produce white precipitate, centrifuge washing white precipitate.In white precipitate, add a certain amount of deionized water, and slowly add wherein rare H of 0.032 M 2sO 4solution also stirs, and white precipitate and dilute sulphuric acid mass ratio are 1:10, then mixed solution are poured in polytetrafluoroethylcontainer container, put into retort furnace.Rise to 200 by room temperature oCrear constant temperature 24 h, heat-up rate is 5 oC/ min.After hydro-thermal reaction finishes, centrifuge washing reaction product to pH value of solution approaches neutral, and then lyophilize obtains Nano bars of alumina.
Take the ultrasonic 200 mL ethanol that are scattered in of 0.15 g Nano bars of alumina, 12 mL water, 1.2 mL ammoniacal liquor, in 0.3 mL tetraethoxy mixing solutions, 30 oCafter lower stirring 24 h, add 0.2 mL 3-(trimethoxysilyl) propyl group-2-methyl-2-acrylate to continue to stir 24 h.Centrifugal, washing after, 60 oCmore than lower vacuum-drying 24 h, obtain the nano-tube that carbon-carbon double bond is modified.
The nanotube that 0.05 g carbon-carbon double bond is modified is scattered in 80 mL acetonitriles, add 0.6 mL vinyl phosphoric acid dimethyl ester, 0.4 mL Vinylstyrene, 0.02 g 2,2'-Diisopropyl azodicarboxylate reacts 80 min under boiling state, will after product separation, clean with ethanol, be distributed in the hydrochloric acid soln of 10 M, in 100 oClower back hydrolysis 24 h, centrifuge washing, to neutral, is finally placed in 60 oCthe above polyvinyl phosphoric acid modification nano-tube that obtains of vacuum oven 24 h.
Gained nanotube length is 1240nm, and diameter is 27nm, and wall thickness is 9nm, and length-to-diameter ratio is 45.9.
Two, the preparation of sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film
A certain amount of nano-tube is scattered in 3 mL nitrogen dimethylformamide solution to ultrasonic 12 h.The sulfonated polyether-ether-ketone that takes 0.7 g is dissolved in 4 mL nitrogen dimethylformamide solution, stirs 24 h.Above-mentioned two kinds of solution mix and blend 2 h are obtained to film-casting liquid.After standing and defoaming, film-casting liquid is poured on clean sheet glass to 60 oClower thermal treatment 12 h, then 80 oClower thermal treatment 12 h.Be cooled to after room temperature, film is taken off from sheet glass, be then placed on acidification 48 h in the sulphuric acid soln of 2 M, be washed till neutrality with deionized water and be placed on 60 oCmore than vacuum oven 24 h, obtain sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film.The consumption that changes nanotube is prepared 4 films, numbering is respectively film 1, film 2, film 3, film 4, and the content that the consumption of polyvinyl phosphoric acid modification nano-tube is respectively nanotube in 0.0175g, 0.035g, 0.0525g, 0.07g, hybridized film is respectively 2.5 wt%, 5 wt%, 7.5 wt%, 10 wt%.
Embodiment 2
Preparation method is consistent with embodiment 1, and difference is: in the preparation process of polyvinyl phosphoric acid modification nano-tube, and rare H that uses 2sO 4concentration be 0.011 M, the nanotube length of preparation is 675nm, diameter is 36nm, wall thickness is 14nm, length-to-diameter ratio is 18.7.Polyvinyl phosphoric acid modification nano-tube consumption is 0.0525 g.In hybridized film, the content of nanotube is 7.5 wt%(films 5).
Embodiment 3
Preparation method is consistent with embodiment 1, and difference is: in the preparation process of polyvinyl phosphoric acid modification nano-tube, do not use rare H 2sO 4, the nanotube length of preparation is 115nm, and diameter is 44nm, and wall thickness is 10nm, and length-to-diameter ratio is 2.6.Polyvinyl phosphoric acid modification nano-tube consumption is 0.0525 g.In hybridized film, the content of nanotube is 7.5 wt%(films 6).
Comparative example
Take 0.7 g sulfonated polyether-ether-ketone and be dissolved in 7 mL nitrogen dimethylformamide solution, stir 24 h.After standing and defoaming, film-casting liquid is poured on clean sheet glass to 60 oClower thermal treatment 12 h, then 80 oClower thermal treatment 12 h.Be cooled to after room temperature, film is taken off from sheet glass, be then placed on acidification 48 h in the sulphuric acid soln of 2 M, be washed till neutrality with deionized water and be placed on 60 oCmore than vacuum oven 24 h, obtain sulfonated polyether-ether-ketone comparative film (film 7).
Testing method
Proton conductivity (level to): the hybridized film of 1 × 2 cm is placed in to fully hydrated of deionized water, film is clipped between two platinum electrodes that interelectrode distance is 1.2 cm, be placed in temperature-humidity conditioner, use electrochemical workstation Impedance measurement, calculate proton conductivity with formula σ=l/AR, wherein l is interelectrode distance, and A is film cross-sectional area, and R is resistance value.
Methanol permeability: adopt barrier film diffusion cell to measure, barrier film diffusion cell is made up of two identical glass half Room of volume.Getting 4 × 4 cm diaphragms is clipped between two glass half Room tightly.Add 30 mL water in left half Room, at the indoor 30 mL methanol solutions that add of right glass half, methanol concentration is 2 M.Under magnetic agitation, spread, take out a certain amount of solution gas chromatograph and detect the concentration of methanol aqueous solution now every 3 min with microsyringe from left glass half Room, methanol permeability (P) can be derived by Fick second law.
Physical strength: adopt electronic tension tester test, draw speed is 2 mm min -1, test diaphragm is 1 × 4 cm specification, tensile strength, and Young's modulus and elongation at break draw from the strain-stress curve recording.
Table 1 is depicted as the prepared film 1 of embodiment, film 2, film 3, film 4, film 5, proton conductivity, methanol permeability, tensile strength, Young's modulus and the elongation at break of the prepared film 7 of film 6 and comparative example.
Figure 2014100924207100002DEST_PATH_IMAGE002
a30 oc, the proton conductivity under 100% relative humidity;
bunder room temperature, test.
From embodiment, in the preparation process of Nano bars of alumina, along with sulfuric acid concentration used reduces, the length-to-diameter ratio of Nano bars of alumina reduces, and then the length-to-diameter ratio of prepared nano-tube reduces.
As seen from the table, compare pure film 7, the proton conduction of hybridized film and alcohol-rejecting ability have lifting more significantly.The length-to-diameter ratio of filling 2.5 wt% is the longest in tri-kinds of nanotubes of 45.9() modified Nano pipe, the mechanical property of hybridized film significantly promotes, continue rising loading level, mechanical property reduces, illustrate that the nanotube of a small amount of (< 2.5 wt%, dispersion effect the is good) big L/D ratios (> 45.9) of filling is conducive to the lifting of mechanical property.
Film 3,5,6 contrast of same loading level, illustrate, along with increase, the proton conductivity of film and the mechanical property rising of the length-to-diameter ratio (length/external diameter) of filled with nanotubes.
Film 3 embodies optimum over-all properties, and the polyvinyl phosphoric acid modification nano-tube that the length-to-diameter ratio of filling as seen 7.5 wt% is 45.9 is optimum process condition.According to gained experiment law, increase the length-to-diameter ratio of modified Nano pipe, loading level regulates between 5-10 wt%, can further optimize the over-all properties of film.

Claims (6)

1. sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film, it is characterized in that take sulfonated polyether-ether-ketone as main body polymer matrix, polyvinyl phosphoric acid modification nano-tube is packing material, and wherein the mass content of polyvinyl phosphoric acid modification nano-tube is 2.5%-10%.
2. the preparation method of sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film as claimed in claim 1, it is characterized in that described polyvinyl phosphoric acid modification nano-tube is synthetic nano-tube using Nano bars of alumina as one dimension template, introduce carbon-carbon double bond with 3-(trimethoxysilyl) propyl group-2-methyl-2-acrylate on nano-tube surface and think that phosphoric acid modification provides avtive spot, then as phosphoric acid modification agent, phosphoric acid modification is carried out in nano-tube surface with vinyl phosphoric acid dimethyl ester, finally with hydrochloric acid by Nano bars of alumina etching, and phosphoric acid ester is converted into phosphate group, form hollow polyvinyl phosphoric acid modification nano-tube.
3. a preparation method for sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film as claimed in claim 2, is characterized in that described Nano bars of alumina is to make aluminium hydroxide and rare H 2sO 4hydro-thermal reaction obtains.
4. a preparation method for sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film as claimed in claim 2, is characterized in that nano-tube is take Nano bars of alumina as template, synthetic take ethanol, water, ammoniacal liquor and tetraethoxy as raw material.
5. the preparation method of sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film as claimed in claim 2, the phosphoric acid modification that it is characterized in that nano-tube is with acetonitrile, vinyl phosphoric acid dimethyl ester, Vinylstyrene, 2,2'-Diisopropyl azodicarboxylate is raw material, under boiling state, reacts and forms.
6. sulfonated polyether-ether-ketone/polyvinyl phosphoric acid modification nano-tube hybridized film as claimed in claim 1 is as the purposes of methanol fuel cell proton exchange membrane, polyvinyl phosphoric acid modification nano-tube can effectively strengthen proton conductivity, alcohol-rejecting ability and the physical strength of hybridized film.
CN201410092420.7A 2014-03-13 2014-03-13 Modified silicon nano-tube hybrid membrane as well as preparation process and application thereof Pending CN103897335A (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN104212153A (en) * 2014-08-27 2014-12-17 天津大学 Sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane as well as preparation method and application of sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane
CN106935665A (en) * 2017-03-15 2017-07-07 常州亿晶光电科技有限公司 A kind of organically-modified CdS doped silicons nanometer tube composite materials and preparation method and purposes
CN114220983A (en) * 2021-12-15 2022-03-22 南京工业大学 Modified membrane based on hollow carbon spheres and preparation method and application thereof
CN114899463A (en) * 2022-05-24 2022-08-12 湖北工程学院 Organic-inorganic composite medium-temperature proton exchange membrane and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104212153A (en) * 2014-08-27 2014-12-17 天津大学 Sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane as well as preparation method and application of sulfonated polyether ether ketone and carboxylated silicon dioxide microsphere hybrid membrane
CN106935665A (en) * 2017-03-15 2017-07-07 常州亿晶光电科技有限公司 A kind of organically-modified CdS doped silicons nanometer tube composite materials and preparation method and purposes
CN106935665B (en) * 2017-03-15 2018-06-08 常州亿晶光电科技有限公司 A kind of organically-modified CdS doped silicons nanometer tube composite materials and preparation method and purposes
CN114220983A (en) * 2021-12-15 2022-03-22 南京工业大学 Modified membrane based on hollow carbon spheres and preparation method and application thereof
CN114220983B (en) * 2021-12-15 2024-01-30 南京工业大学 Modified membrane based on hollow carbon spheres and preparation method and application thereof
CN114899463A (en) * 2022-05-24 2022-08-12 湖北工程学院 Organic-inorganic composite medium-temperature proton exchange membrane and preparation method thereof
CN114899463B (en) * 2022-05-24 2024-04-26 湖北工程学院 Organic-inorganic composite medium-temperature proton exchange membrane and preparation method thereof

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