CN104638283B - Electrostatic spinning method for preparing sponge-shaped Nafion membrane - Google Patents
Electrostatic spinning method for preparing sponge-shaped Nafion membrane Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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Abstract
The invention provides an electrostatic spinning method for preparing a sponge-shaped Nafion membrane. The electrostatic spinning technology is a method for enabling a charged macromolecular solution (or melt) to have flowing deformation in an electrostatic field and obtaining a fibrous material by virtue of volatilization of a solvent or cooling of the melt. By adopting the electrostatic spinning method, while an active area is guaranteed, the resistance loss of the membrane can be maximally reduced, the specific surface area is high, and the battery performance can be remarkably improved.
Description
Technical field
The present invention relates to a kind of electrospinning process for preparing spongy Nafion membrane.
Background technology
Proton Exchange Membrane Fuel Cells is suitable for various environmental weather conditions and has longer service life, is ideal
Movable power source, be most have research space and development prospect a kind of electrical source of power.PEM is used as PEM
The core component of fuel cell, it has the advantages that proton conductivity is high and chemical stability is good.But its expensive price and
Higher methanol permeability and some inferior positions but hinder its industrialized development significantly.Therefore, improve battery at high temperature
Proton conductivity, reduce the permeability of methanol, reduces cost, and improve the utilization rate of catalyst, increase service life,
Very important effect is played to developing DMFCs.
Nafion membrane possesses many advantages such as proton conductivity height, good, the heat-resist and excellent machinery of chemical stability
Performance etc..But the shortcoming of Nafion membrane itself also constrains the large-scale commercial of fuel cell：1st, as film quality is passed through
Rate is affected by water content in film, and fuel battery temperature is raised, and the proton conductivity of film is seriously reduced；2nd, film synthesis high cost；3、
The higher work efficiency for reducing battery of methanol permeability, Poisoning cathode catalyst.The performance for improving Nafion membrane at present is main
From from the aspect of following two：On the one hand battery proton conductivity at high temperature is improved, the infiltration of methanol is on the other hand reduced
Rate.In order to solve these problems, it is at present main by modified Nafion membrane realizing transformation.Modify including electrostatic self-assembled
Nafion membrane, chemical crosslinking etc..And the core of all Modified Membrane is raising methanol permeability, improves Proton conducting under high temperature
Rate, reduces cost etc..Therefore the electrical conductivity of expendable film is come to reduce methanol to the method for the permeability of film be worthless.And adopt
Cationic polymer doping prepares PEM, really the same with the method for chemical crosslinking, be so that additive with
There is chemical reaction in the part sulfonate radical in film, make these sulfonate radicals swelling rate being fixed up to reduce film steadily cause first
Alcohol permeability obtains a certain degree of reduction.From for theoretical angle, the method for the above all reduces methanol well to film
Penetrating power, but additive simultaneously also makes a certain degree of decline of electrical conductivity of film；When being added inorganic nano to film
During particle, prioritizing selection should be the inorganic substances with certain proton conductivity, such as Sc+Deng, but so equally deposit
Problem be possible to affect the life-span of film because that what is selected is easily easily lost in the operation of battery again；When adopting thing
When compound other the infiltrative materials that can reduce methanol of reason prepare film, whether film there is certain proton conductivity to be should
This is noticeable；It is worth simultaneously advocating, if the modification to film is simply related to the surface of film, additive will not then enter
Enter the performance of the internal influence film of film.If the performance of film would not be affected in film surface using self-assembling nanoparticles, modification
The proton conductivity of caudacoria does not have very big decline.
Proton Exchange Membrane Fuel Cells had adopted phenolic resin sulfonate film, polytrifluorostyrene and perfluor so far
Sulfonate film etc. is several.Wherein the solid electrolyte of most suitably used PEMFC is perfluor sulphur PEM at present.But perfluoro sulfonic acid membrane
High cost, conductivity water content the scale of PEMFC is greatly limited the shortcomings of affecting big, so needing badly to perfluoro sulfonic acid membrane
It is improved and develops novel proton exchange membranes.
At present, the country there is no and again to which carry out mechanical enhancer after spongy Nafion membrane with regard to be prepared using electrostatic spinning
Patent documentation.Its Patent《A kind of preparation method of the polymer nanofibre film containing perfluorinated sulfonic acid》(CN 103469352A)
Inorganic intensifying method is used, the polymer nanofibre film containing perfluorinated sulfonic acid for preparing is soaked in an acidic solution.Specially
Profit《A kind of preparation method of Nafion nanometer filter film》(CN 102618944A) is the Nafion solution using 5wt% and adds
Plus a small amount of PEO, intensive treatment is not carried out afterwards.
The content of the invention
In order to solve the above problems, the present invention provides a kind of electrospinning process for preparing spongy Nafion membrane, wherein
Electrostatic spinning technique is to make powered macromolecular solution (or melt) flow deformation in electrostatic field, and the volatilization of Jing solvents or melt are cold
But solidify, so as to obtain a kind of method of fibrous material, it can be while its effective area be ensured, being capable of maximum journey
Reduce the ohmic loss of film on degree；With preferable high-ratio surface, battery performance can be significantly improved.In fact, with nanometer
Technology is developed rapidly, and electrostatic spinning film technique obtained increasingly being widely applied.
The present invention is achieved through the following technical solutions：
Spongy Nafion membrane with PAN as auxiliary agent is prepared by method of electrostatic spinning, is changed auxiliary agent content and is prepared by voltage
The excellent spongy Nafion membrane of structure.Then mechanical performance intensive treatment is carried out to spongy Nafion membrane, with spongy
Nafion membrane is scaffold base, strengthens the mechanical performance of spongy Nafion membrane using electrostatic spraying processes.Its bursting stress reaches
25.67MP has been arrived, and 3.85MP has been increased than pure Nafion membrane.Then to reinforcing after spongy Nafion membrane pattern and performance
Further test analysis are done.Test result shows：Spongy Nafion membrane after reinforcing have more excellent moisture content,
Proton conductivity and methanol permeability under tensile property and high temperature.
It is an object of the invention to provide a kind of electrospinning process for preparing spongy Nafion membrane, including following step
Suddenly：
1., the preparation of spinning liquid：Polyacrylonitrile (PAN) is dissolved in into N,N-dimethylacetamide (DMAc), matter is then dissolved in
During amount fraction is 10% Nafion solution, the spinning liquid that polyacrylonitrile (PAN) concentration is 5wt%～15wt% is configured to；
2., the preparation of spongy Nafion membrane：The spinning liquid that 1. step is obtained stirs 24h on magnetic stirring apparatuss to molten
Liquid clear homogeneous, are conducted in syringe, carry out electrostatic spinning by electrostatic spinning apparatus and prepare spongy Nafion membrane,
Spinning voltage 10KV～15KV；
3., the mechanical enhancer of film：The spongy Nafion membrane that 2. step obtains is fixed between two pieces of glass plates,
After being dried 5 hours in 130 DEG C of vacuum drying ovens, using dried spongy Nafion membrane as new reception device, quality is used
Fraction is 20% concentration Nafion solution electrostatic spray 30min, places 2h at ambient temperature, then dry through 130 DEG C of vacuum
Dry 40 minutes, then repeatedly after electrostatic spray 30min, vacuum drying, heat treatment, the mechanical enhancer of spongy Nafion membrane is complete
Into；
4., the post processing of film：Spongy Nafion membrane after the reinforcing that 3. step is obtained successively isopropanol, 80 DEG C
5%H2O2Solution and 80 DEG C of 0.5mol/LH2S04Process in the deionized water of solution and 80 DEG C after 0.5h carries out remove impurity, be dried.
Further, in above-mentioned technical proposal, 2., the condition of electrostatic spinning is the step：Syringe advances speed
It is 10～15cm for the distance between 0.2～2.0ml/h, spinning head internal diameter 0.7mm, reception device and electrode.
Further, in above-mentioned technical proposal, 3., the condition of electrostatic spinning is the step：Voltage is 10～15KV,
Syringe propulsion speed is 0.2～2.0ml/h, spinning head internal diameter 0.7mm, the distance between reception device and electrode for 10～
15cm。
Invention beneficial effect
The present invention is adopted by auxiliary agent of PAN and prepares the homogeneous spongy Nafion membrane of shape characteristic using electrospinning process,
Then electrostatic spray machinery intensive treatment is carried out for 20% Nafion solution with concentration concentration.Sponge after Experimental Characterization reinforcing
Under shape Nafion membrane mechanical performance and high temperature, proton conductivity and moisture content have different degrees of raising, while methanol oozes
Rate is also decreased obviously thoroughly, and this experimental result significantly improves the efficiency of fuel cell.Develop a kind of new based on Static Spinning
The method that silk technology prepares spongy Nafion membrane.
Description of the drawings
8 width of accompanying drawing of the present invention,
Fig. 1 a are the scanning electron microscope (SEM) photographs of spongy Nafion membrane prepared by embodiment 1；1b is the spongy of the preparation of embodiment 2
The scanning electron microscope (SEM) photograph of Nafion membrane；
Fig. 2 a are the scanning electron microscope (SEM) photographs of spongy Nafion membrane prepared by embodiment 3；2b is the spongy of the preparation of embodiment 4
The scanning electron microscope (SEM) photograph of Nafion membrane；2c is the scanning electron microscope (SEM) photograph of spongy Nafion membrane prepared by embodiment 5；
Fig. 3 is spongy Nafion membrane fiber bundle diameters and PAN contents prepared by embodiment 3, embodiment 4 and embodiment 5
Curve；
Fig. 4 a are the electron microscopes of spongy Nafion membrane pattern prepared by embodiment 4；Fig. 4 b, 4d are prepared by embodiment 4
The electron microscope of the spongy Nafion membrane after reinforcing；Fig. 4 c are that the spongy Nafion membrane after reinforcing prepared by embodiment 4 is transversal
The electron microscope in face；
Fig. 5 is Nafion membrane, the spongy Nafion membrane plot of water cut figure of the preparation of embodiment 4；
Fig. 6 is Nafion membrane, the proton conductivity of the spongy Nafion membrane of the preparation of embodiment 4 and temperature curve；
Fig. 7 is Nafion membrane, the methanol permeability of the spongy Nafion membrane of the preparation of embodiment 4 and temperature curve；
Fig. 8 is the curve of crossover of methanol side concentration changes with time.
Specific embodiment
Following nonlimiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
Embodiment 1
PAN compounding agent solutions are prepared：Quantitative polyacrylonitrile (PAN) is weighed with electronic analytical balance and pours glass reagent bottle into
In, appropriate N,N-dimethylacetamide (DMAc) dissolving PAN is taken, and makes its concentration be 10%, be placed on magnetic stirring apparatuss and stir
Mix 24h fully to dissolve up to PAN, obtain PAN compounding agent solutions.
Quantitative Nafion (5wt%) solution is weighed in weighing botle, 60 DEG C in vacuum drying oven so as to evaporation section alcohol
After solvent, the Nafion solution of 10wt% is obtained.Add the solution of Nafion (10wt%) to PAN compounding agent solutions, be configured to PAN
Concentration is the spinning liquid of 10wt%, the spinning liquid for having configured is stirred 24h to solution clear homogeneous on magnetic stirring apparatuss, by which
Import in syringe, regulation voltage is 10KV, and the distance between spinning electrode rod to receiver board is 15cm, will preparation sponge
Shape Nafion membrane is dried at room temperature for more than 24h, sees the form of the spongy Nafion membrane of Fig. 1 a scanning electron microscopic observations.
Embodiment 2
Quantitative Nafion (5wt%) solution is weighed in weighing botle, 60 DEG C in vacuum drying oven so as to evaporation section alcohol
After solvent, the Nafion solution of 10wt% is obtained.Add the solution of Nafion (10wt%) to PAN compounding agent solutions, be configured to PAN
Concentration is the spinning liquid of 5wt%, the spinning liquid for having configured is stirred 24h to solution clear homogeneous on magnetic stirring apparatuss, by which
Import in syringe, regulation voltage is 12KV, and the distance between spinning electrode rod to receiver board is 15cm, will preparation sponge
Shape Nafion membrane is dried at room temperature for more than 24h, sees the form of the spongy Nafion membrane of Fig. 1 b scanning electron microscopic observations.
Embodiment 3
Quantitative Nafion (5wt%) solution is weighed in weighing botle, 60 DEG C in vacuum drying oven so as to evaporation section alcohol
After solvent, the Nafion solution of 10wt% is obtained.Add the solution of Nafion (10wt%) to PAN compounding agent solutions, be configured to PAN
Concentration is the spinning liquid of 15wt%, the spinning liquid for having configured is stirred 24h to solution clear homogeneous on magnetic stirring apparatuss, by which
Import in syringe, regulation voltage is 12.1KV, and the distance between spinning electrode rod to receiver board is 15cm, will preparation sea
Continuous shape Nafion membrane is dried at room temperature for more than 24h, sees the form of the spongy Nafion membrane of Fig. 2 a scanning electron microscopic observations.
Embodiment 4
Quantitative Nafion (5wt%) solution is weighed in weighing botle, 60 DEG C in vacuum drying oven so as to evaporation section alcohol
After solvent, the Nafion solution of 10wt% is obtained.Add the solution of Nafion (10wt%) to PAN compounding agent solutions, be configured to PAN
Concentration is the spinning liquid of 10wt%, the spinning liquid for having configured is stirred 24h to solution clear homogeneous on magnetic stirring apparatuss, by which
Import in syringe, regulation voltage is 10KV, and electrostatic spinning 5h, the distance between spinning electrode rod to receiver board are 15cm,
The spongy Nafion membrane for preparing is dried at room temperature for into more than 24h, Fig. 2 b, the spongy Nafion of Fig. 4 a scanning electron microscopic observations is seen
The form of film.
The spongy Nafion membrane for obtaining is fixed between two pieces of glass plates, 5 is dried in 130 DEG C of vacuum drying ovens little
Shi Hou, it is using dried spongy Nafion membrane as new reception device, molten with the concentration Nafion that mass fraction is 20%
Liquid electrostatic spray 30min, is shown in Fig. 4 b, the form of the spongy Nafion membrane of Fig. 4 c scanning electron microscopic observations.Place at ambient temperature
2h, then through the drying 40 minutes of 130 DEG C of vacuum, then after electrostatic spray 30min, vacuum drying, heat treatment, it is strong by what is obtained
Spongy Nafion membrane after change is successively in isopropanol, 80 DEG C of 5%H2O2Solution and 80 DEG C of 0.5mol/LH2S04Solution and 80
DEG C deionized water in process after 0.5h carries out remove impurity, be dried.See the form of the spongy Nafion membrane of Fig. 4 d scanning electron microscopic observations.
Fig. 4 a can show that its fibre diameter is about 200～300nm, intersect and shuttle, so as to constitute aperture between each fiber
For 1 μm or so of perforated membrane.As schemed, shown in b, figure c, to can be seen that fiber-reinforced composite film surface from the SEM photograph on film surface
All smooth, compact structure, no obvious hole are present, and no clear opening, structure are homogeneous, illustrate that cellosilk is distributed in film
Uniformly.Reasonable effect has also been obtained with spongy Nafion membrane prepared by electrostatic spray.Can be seen that from prepared by figure d
Electrostatic spray 1h after film amplify 10000 times when, it can be seen that there is slight projection on film surface, is effectively increased the table of film
Area.All smooth, the compact structure that can be seen that fiber-reinforced composite film surface from the SEM photograph on film surface, without obvious
Hole exist, no clear opening, structure be homogeneous, illustrates that cellosilk is evenly distributed in film.With the spongy of electrostatic spray preparation
Nafion membrane has also obtained reasonable effect.
Embodiment 5
Quantitative Nafion (5wt%) solution is weighed in weighing botle, 60 DEG C in vacuum drying oven so as to evaporation section alcohol
After solvent, the Nafion solution of 10wt% is obtained.Add the solution of Nafion (10wt%) to PAN compounding agent solutions, be configured to PAN
Concentration is the spinning liquid of 5wt%, the spinning liquid for having configured is stirred 24h to solution clear homogeneous on magnetic stirring apparatuss, by which
Import in syringe, regulation voltage is 14.5KV, and the distance between spinning electrode rod to receiver board is 15cm, by preparation
Spongy Nafion membrane is dried at room temperature for more than 24h, sees the form of the spongy Nafion membrane of Fig. 2 c scanning electron microscopic observations.
1.1 characterizing method
This experiment adopts NEC company JSM-6300LV types scanning electron microscope observation sponge- in every possible way
The various features image of Nafion membrane surface and sample surfaces, running voltage is 20kV.
1.2 physical and chemical performances are tested
The test of moisture content be by reinforcing after spongy Nafion membrane at 80 DEG C be dried to constant weight, use electronic analysis day
Flat initial mass W0 for claiming sample quality, after spongy Nafion membrane is placed on into deionized water immersion, soak at a certain temperature
To 24h, go out the water that quick filter paper removes spongy Nafion membrane remained on surface, its weight in wet base is called W1, then calculated.
Moisture content computing formula is：
Proton conductivity is measured, AC impedance parameter by CHI66C type electrochemical workstations (Shanghai Chen Hua instrument companies)
It is set to sweep limitss：10hz-1000khz, disturbance voltage are 10mv, measure the ac impedance spectroscopy of spongy Nafion membrane.
Tensile property is to apply quiet to sample film by HD-615-S paper pull machines (Haidah Instrument Ltd.)
State tensile load carries out tensile strength test, draw speed 60mm.min-l。
The diameter of 2.1 membrane fibers
The fiber of the spongy Nafion membrane that Nafion Concentration of precursor solution is prepared when PAN is 15wt% is straight as shown in Figure 3
Footpath is flat to be about 260nm, and then fibre diameter constantly reduces with the reduction of PAN concentration, when PAN concentration is 5wt%, film
Fibre spinning has fiber and crosslinks, and measurement its diameter for randomly selecting that 100 fibers do not crosslink has reached 180nm
Left and right.The cellosilk of 200nm or so is reached when PAN concentration is 10wt%, photo can be seen that diameter is very uniform, arrangement rule
Whole, surface is smooth.So when PAN concentration is 10wt%, spongy Nafion membrane is that shape characteristic is best.
Spongy Nafion membrane fiber bundle diameters prepared by 1 embodiment of table 3,4,5
| PAN concentration (%) | Electric field strength (Kv/cm) | Cellosilk average diameter (nm) | |
| Embodiment 3 | 15 | 12.1kv/15cm | 260 |
| Embodiment 4 | 10 | 10kv/15cm | 200 |
| Embodiment 5 | 5 | 14.5kv/15cm | 180 contain an a large amount of beading |
Less than 2.2 test be to reinforcing after spongy Nafion membrane characterizing：
2.2.1 the test of moisture content
| Reagent name | Purity/model | The place of production |
| Nafion membrane | —— | Du Pont companies of the U.S. |
| Dehydrated alcohol | Analysis is pure | Tianjin Fu Yu Fine Chemical Co., Ltd |
| N,N-dimethylacetamide | Analysis is pure | Tianjin Fu Yu Fine Chemical Co., Ltd |
Fig. 5 compares pure Nafion membrane, spongy Nafion membrane water-cut variation situation.With the rising of temperature,
Nafion membrane, the moisture content of two kinds of spongy Nafion membrane are being gradually stepped up.At a relatively high temperature, it is spongy
Nafion membrane is faster than the moisture content growth of Nafion membrane.In 85 DEG C of temperature, the water content of spongy Nafion membrane reaches
32.37%, this is about 1.2 times of pure Nafion membrane.
2.2.2 proton conductivity test
Fig. 6 is the proton conductivity of spongy Nafion membrane under different temperatures.It can be seen that with temperature liter
Height, the electrical conductivity of Nafion membrane are increased；The proton conductivity of spongy Nafion membrane is less than Nafion at the same temperature
Film.This is because certain obstacle can be formed to proton conducting channel after adding PAN, reduce electrical conductivity, but it is strong due to selecting
The high Nafion solution of degree specific surface area as reinforcement and huge, with the raising of temperature, reduces reinforcement to sea
The impact of continuous shape Nafion membrane proton conductivity.And make the thickness of film thinner as spongy Nafion membrane can increase, reduce
The internal resistance of film, so spongy Nafion membrane proton conductivity fall compared with Nafion membrane is little.When PAN additions
During 10wt%, proton conductivity of the spongy Nafion membrane at 65 DEG C is 0.0l6s/cm, suitable with Nafion membrane.Work as temperature
65 DEG C to 80 DEG C of scopes when, the proton conductivity of spongy Nafion membrane is better than pure Nafion membrane.
2.2.3 tensile property test
Table 2 sets forth the Nafion membrane of purchase, the tensile strength data of spongy Nafion membrane prepared by embodiment 4
Analysis, comparing increases the mechanical performance of polymeric film due to the spraying of Nafion solution, so spongy Nafion membrane is than pure
Nafion membrane tensile strength is high.Reason possibly electrostatic field force to be overcome the surface tension of spinning precursor liquid, cellosilk have received
Sufficiently stretch, and spongy Nafion membrane surface light sliding cutting is homogeneous, a no beading occur.So fibre bundle has drawing well
Stretch.Filling heat treatment through Nafion solution further enhances the mechanical performance of film again.
The mechanical strength of 2 film of table
2.2.4 methanol permeability test
The methanol crossover experiment of film, is tested using the homemade gas diffusion pond of laboratory, gas at normal temperatures and pressures
During diffusion cell is referring to patent CN102903937A, U-shaped Liquid-phase reactor.There are 70ml methanol aqueous solutions and 70ml deionizations respectively
Water.Cutting a certain size film to be measured, is inserted between the container of left and right, then starts timing, and stirs while opening two magnetic force
Device is mixed, left and right indoor solution mix homogeneously all the time in test process is made, while reduce film both sides concentration polarization, at interval of one
Container on the right of fixed time measures 0.5ml sample solutions, and internal standard substance ethanol is added after weighing.Finally with gas chromatograph pair
Sample is measured.
The measure of methanol permeability
When assuming t=0, two Room concentration of left and right is respectively C0And L0, during t=t, both sides concentration is respectively CtAnd Lt, the face of film
Product is A, and the molar flow of methanol is molcm2s-1For X
Then：
(2.4)
Hypothesis sets up static equilibrium, and X is at a time a constant, is had：
(2.5)
Finally give：
(2.6)
Then according to formula 2.6.WillIt is plotted against time, gained slope is PEM first
The infiltration coefficient of alcohol.
Fig. 8 is the curve of typical crossover of methanol side concentration changes with time.
Fig. 7 compares the methanol crossover system of spongy Nafion membrane prepared by Nafion membrane and embodiment 4 under different temperatures
Number.It can be seen that under room temperature, during PAN contents 10wt%, spongy Nafion membrane methanol permeability is 4.78x10-7, than
The 1.17x10 of Nafion membrane-6An order of magnitude is reduced, the alcohol-rejecting ability of Nafion membrane after this explanation addition PAN, is improved.By
It is embedded in the form of electrostatic spinning in the ion cluster of reverse micelle network structure of Nafion membrane in PAN, reduces proton transport
Passage, so hindering penetrating for part methanol.And the methanol permeability of spongy Nafion membrane and Nafion membrane is equal
Increase with the rising of temperature.This is because with the rising of temperature, the transmission speed of proton can be accelerated, while proton is carried
The transmission speed of water also accelerate, and the polarity of hydrone and methanol molecules size is much like, and this also causes to a certain extent
The quickening of methanol migration, causes methanol permeability to become big.
The present invention is complicated for Nafion membrane synthesis, and high cost and moisture content are low, and proton conductivity difference and catalyst make
Started with the low problem of efficiency, be prepared for spongy Nafion membrane first, and its performance enhancement made with the method for electrostatic spray.It is logical
Addition polyacrylonitrile macromolecule polymeric material is crossed by high-voltage electrostatic spinning machine, adjusting process parameter, electrostatic spray will be spongy
Nafion membrane has done further optimization, as the jet-action of Nafion solution causes fiber reinforced composite film to have preferably
Mechanical performance and dimensional stability.
The moisture content of the spongy Nafion membrane after reinforcing, proton conductivity and tensile property increase.Under room temperature, sea
The electrical conductivity of continuous shape Nafion membrane is 10-3More than m, when 70 DEG C, the proton conductivity of spongy Nafion membrane is substantially higher than pure
The proton conductivity of Nafion membrane.
Claims (3)
1. a kind of electrospinning process for preparing spongy Nafion membrane, it is characterised in that comprise the following steps：
1., the preparation of spinning liquid：Polyacrylonitrile is dissolved in into N,N-dimethylacetamide, is then dissolved in 10%Nafion solution,
It is configured to the spinning liquid that polyacrylonitrile concentration is 5wt%～15wt%；
2., the preparation of spongy Nafion membrane：It is saturating to solution that the spinning liquid that 1. step is obtained stirs 24h on magnetic stirring apparatuss
It is bright uniform, be conducted in syringe, electrostatic spinning is carried out by electrostatic spinning apparatus and prepare spongy Nafion membrane, spinning
Voltage 10KV～15KV；
3., the mechanical enhancer of film：The spongy Nafion membrane that 2. step obtains is fixed between two pieces of glass plates, at 130 DEG C
After being dried 5 hours in vacuum drying oven, using dried spongy Nafion membrane as new reception device, with mass fraction it is
20% concentration Nafion solution electrostatic spray 30min, places 2h at ambient temperature, then through 130 DEG C of vacuum, 40 points of drying
Clock, then repeatedly after electrostatic spray 30min, vacuum drying, heat treatment, the mechanical enhancer of spongy Nafion membrane is completed；
4., the post processing of film：Spongy Nafion membrane after the reinforcing that 3. step is obtained successively isopropanol, 80 DEG C 5%
H2O2Solution and 80 DEG C of 0.5mol/LH2S04Process in the deionized water of solution and 80 DEG C after 0.5h carries out remove impurity, vacuum drying.
2. method according to claim 1, it is characterised in that：2., the condition of electrostatic spinning is the step：Syringe is pushed away
It is 10～15cm to enter speed for the distance between 0.2～2.0ml/h, spinning head internal diameter 0.7mm, reception device and electrode.
3. method according to claim 1, it is characterised in that：3., the condition of electrostatic spinning is the step：Voltage is 10
～15KV, syringe propulsion speed is the distance between 0.2～2.0ml/h, spinning head internal diameter 0.7mm, reception device and electrode
For 10～15cm.
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| CN101768284B (en) * | 2010-01-25 | 2011-11-23 | 东北大学 | Preparation method of perfluorinated high-temperature proton-conductor composite membrane |
| CN102021677B (en) * | 2010-10-13 | 2013-07-03 | 清华大学 | Preparation method for carbon nanofiber containing transition metal and nitrogen element and application of carbon nanofiber in fuel-cell catalysts |
| CN102054990A (en) * | 2010-12-06 | 2011-05-11 | 常熟理工学院 | Method for preparing nano electro-catalyst for anode of ethanol fuel cell |
| CN102427141B (en) * | 2011-12-01 | 2013-11-20 | 中山大学 | Composite proton exchange membrane and preparation method thereof |
| CN102618944B (en) * | 2012-03-28 | 2014-09-17 | 哈尔滨工业大学 | Method for preparing Nafion nanometer filter film |
| CN103469352A (en) * | 2012-06-06 | 2013-12-25 | 华东理工大学 | Preparation method of polymer nanofiber membrane containing perfluorinated sulfonic acid |
| CN102716769A (en) * | 2012-07-02 | 2012-10-10 | 华东理工大学 | Preparation method of perfluorosulfonic acid nano composite fiber catalyst for esterification reaction |
| CN103263855A (en) * | 2013-06-04 | 2013-08-28 | 北京巨龙博方科学技术研究院 | Method for preparing ion exchange membrane by electrostatic spinning |
| CN103413947B (en) * | 2013-08-27 | 2015-07-22 | 武汉理工大学 | Fuel cell ordered porous nano-fiber single electrode, membrane electrode and preparation method |
| CN104103794B (en) * | 2014-08-05 | 2016-02-17 | 厦门大学 | A kind of preparation method of compound proton exchange membrane |
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2015
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