CN106784941A - A kind of PEM with cross-film distribution nanofibrous structures and preparation method thereof - Google Patents
A kind of PEM with cross-film distribution nanofibrous structures and preparation method thereof Download PDFInfo
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- CN106784941A CN106784941A CN201710022564.9A CN201710022564A CN106784941A CN 106784941 A CN106784941 A CN 106784941A CN 201710022564 A CN201710022564 A CN 201710022564A CN 106784941 A CN106784941 A CN 106784941A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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Abstract
The invention provides a kind of preparation method of the PEM with cross-film distribution nanofibrous structures, with sulfonation non-fluorine hydrocarbon polymer as raw material, proton conductive nano fibrofelt is prepared using solution jet spinning method；With thermoplastic resin as raw material, substrate nano fibrofelt is prepared using solution jet spinning method；By substrate nano fibrofelt and proton conductive nano fibrofelt laying into sandwich shape nanofiber mats；The substrate nano fibrofelt is sandwich layer, and proton conductive nano fibrofelt is surface layer；By sandwich shape nanofiber mats hot pressing, obtain being distributed with cross-film the PEM of nanofibrous structures.The present invention makes matrix be sufficient filling with the space of proton conductive nano fiber using pressure sintering, the nanofiber prepared using solution spinning has three-dimensional crimp characteristic this feature, the proton conductive nano fiber after hot pressing is set to form obvious cross-film distributed architecture, proton transmitting channel is extended, the proton transport ability of PEM is improve.
Description
Technical field
It is more particularly to a kind of that there is cross-film to be distributed nanofiber knot the present invention relates to a kind of technical field of PEM
PEM of structure and preparation method thereof.
Background technology
Fuel cell (Fuel cell) can will be stored in fuel and oxidant as a kind of novel energy conversion equipment
In chemical energy be converted into electric energy, energy utilization rate is high, has broad application prospects.In various types of fuel
In battery, DMFC (Direct Methanol Fuel Cell, DMFC) is steamed using methanol aqueous solution or methyl alcohol
Vapour is that fuel supplies source, have the advantages that battery structure is simple, raw material is easily stored and transports and can started quickly at low temperature, in recent years
Come the swift and violent development for obtaining.
PEM (Proton Exchange Membrane, PEM) is the core component of DMFC
One of, for the conduction of proton provides passage, the diffusion of methyl alcohol is prevented, and play a part of to separate power cell anode-cathode, it
Performance quality directly affects the performance of fuel cell.In recent years, the nanofiber technology of preparing with electrostatic spinning technique as representative
For the proton transfer passage design of PEM provides new Research Thinking.By polyelectrolyte spinning for nanofiber or
The immobilized electrolyte molecule of nanofiber surface, is capable of achieving proton transfer group and is enriched with distribution along the orientation in nanofiber direction, with
Proton transfer long-channel can be formed in film after film forming matter is compound, so as to improve the proton conduction property of film.
Prepared by conventional electrostatic spinning nano fiber glass composite film plate knife coating and solution dipping method, due to Static Spinning Nanowire
It is tightly combined between dimension, film forming matter is difficult filling completely in fibre gap, and composite membrane both side surface is easily generated and is free of nanometer
The proton conductivity of fiber weak " transmission barrier layer ", so as to cause the decline of the proton conductivity of composite membrane.
The content of the invention
In view of this, present invention aim at provide it is a kind of with cross-film distribution nanofibrous structures PEM and
Its preparation method, improves the proton conductivity of PEM, reduces methanol permeability.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of the PEM with cross-film distribution nanofibrous structures, including with
Lower step：
With sulfonation non-fluorine hydrocarbon polymer as raw material, proton conductive nano fibrofelt is prepared using solution jet spinning method；
With thermoplastic resin as raw material, substrate nano fibrofelt is prepared using solution jet spinning method；
By the substrate nano fibrofelt and proton conductive nano fibrofelt spacer stack laying into sandwich shape nanofiber
Felt；The substrate nano fibrofelt is sandwich layer, and the proton conductive nano fibrofelt is surface layer；
By the sandwich shape nanofiber mats hot pressing, obtain being distributed with cross-film the PEM of nanofibrous structures.
Preferably, the sulfonation non-fluorine hydrocarbon polymer is sulfonated polyether sulfone, sulfonated polyether-ether-ketone, sulfonate polybenzimidazole
With the mixture of one or more in sulfonated polyimide.
Preferably, the thermoplastic resin is the mixture of one or more in Kynoar, polypropylene and polyester.
Preferably, the thickness before the proton conductive nano fibrofelt hot pressing is 50~150 μm；The substrate nano fiber
Thickness before felt hot pressing is 50~100 μm.
Preferably, the quality of the sandwich shape nanofiber mats mesostroma nanofiber mats is that sandwich shape nanofiber mats are total
The 10~40% of quality.
Preferably, the temperature of the hot pressing is 170~190 DEG C；The pressure of the hot pressing is 5~15MPa；The hot pressing
Time is 20~60min.
Preferably, preheating is also included before the hot pressing；The temperature of the preheating is 120~160 DEG C；The time of the preheating
It is 1~8min.
The invention provides prepared by preparation method described in a kind of such scheme nanofibrous structures are distributed with cross-film
PEM, including thermoplastic resin matrix layer and the proton conductive nano fiber of cross-film distribution.
Preferably, the thickness of the PEM is 40~120 μm.
The invention provides a kind of preparation method of the PEM with cross-film distribution nanofibrous structures, including with
Lower step：With sulfonation non-fluorine hydrocarbon polymer as raw material, proton conductive nano fibrofelt is prepared using solution jet spinning method；With
Thermoplastic resin is raw material, and substrate nano fibrofelt is prepared using solution jet spinning method；By the substrate nano fibrofelt and
Proton conductive nano fibrofelt spacer stack laying is into sandwich shape nanofiber mats；The substrate nano fibrofelt is sandwich layer, institute
Proton conductive nano fibrofelt is stated for surface layer；By the sandwich shape nanofiber mats hot pressing, obtain being distributed Nanowire with cross-film
Tie up the PEM of structure.The present invention can be in proton Conductive fiber after melting substrate nano fibrofelt using pressure sintering
Even dispersion is simultaneously sufficient filling with space, and the nanofiber prepared using solution spinning has obvious three-dimensional crimp characteristic, and this is special
Point, makes proton conductive nano fiber stretch out film surface, forms obvious cross-film distributed architecture, it is to avoid in the generation of film both side surface not
Containing nanofiber " transmission barrier layer ", proton transmitting channel is effectively extended, improve the proton transport energy of PEM
Power；And the present invention is by the use of thermoplastic resin as internal matrix, effective resistance alcohol layer is formed, effectively reduce proton exchange
The methanol permeability of film.
The invention provides prepared by preparation method described in a kind of such scheme nanofibrous structures are distributed with cross-film
PEM, with good proton conductivity and alcohol-resistant performance.Test result indicate that, what the present invention was provided divides with cross-film
The proton conductivity of the PEM of cloth nanofibrous structures can reach 0.178S/cm, and methanol permeability as little as 0.34 ×
10-8cm2/s。
Brief description of the drawings
Fig. 1 is the electron microscope observation figure of the gained Surface modification of proton exchange membrane of the embodiment of the present invention 1；
Fig. 2 is the electron microscope observation figure of the gained PEM section of the embodiment of the present invention 1；
Fig. 3 is the electron microscope observation figure of the gained Surface modification of proton exchange membrane of the embodiment of the present invention 2；
Fig. 4 is the electron microscope observation figure of the gained Surface modification of proton exchange membrane of the embodiment of the present invention 3；
Fig. 5 is the PEM structural representation of the embodiment of the present invention.
Specific embodiment
The invention provides a kind of preparation method of the PEM with cross-film distribution nanofibrous structures, including with
Lower step：
With sulfonation non-fluorine hydrocarbon polymer as raw material, proton conductive nano fibrofelt is prepared using solution jet spinning method；
With thermoplastic resin as raw material, substrate nano fibrofelt is prepared using solution jet spinning method；
By the substrate nano fibrofelt and proton conductive nano fibrofelt spacer stack laying into sandwich shape nanofiber
Felt；The substrate nano fibrofelt is sandwich layer, and the proton conductive nano fibrofelt is surface layer；
By the sandwich shape nanofiber mats hot pressing, obtain being distributed with cross-film the PEM of nanofibrous structures.
It is fine that the present invention prepares proton conductive nano with sulfonation non-fluorine hydrocarbon polymer as raw material, using solution jet spinning method
Dimension felt.In the present invention, the sulfonation non-fluorine hydrocarbon polymer is preferably sulfonated polyether sulfone (SPES), sulfonated polyether-ether-ketone
(SPEEK), the mixture of one or more in sulfonate polybenzimidazole (SPBI) and sulfonated polyimide (SPI)；It is described mixed
Compound is preferably 2~3 kinds of mixtures of sulfonation non-fluorine hydrocarbon polymer, more preferably sulfonated polyether sulfone (SPES) and sulfonated polyether
The mixture or sulfonated polyether of the mixture, sulfonate polybenzimidazole (SPBI) and sulfonated polyimide (SPI) of ether ketone (SPEEK)
The mixture of ether ketone (SPEEK) and sulfonate polybenzimidazole (SPBI).In the present invention, the proton conductive nano fibrofelt heat
Thickness before pressure is preferably 50~150 μm, more preferably 80~120 μm；The grammes per square metre of the proton conductive nano fibrofelt is preferred
It is 15~45g/m2, more preferably 25~35g/m2；The fibre diameter of the proton conductive nano fibrofelt is preferably 50~
800nm, more preferably 100~600nm, most preferably 200~300nm.
Sulfonation non-fluorine hydrocarbon polymer is preferably configured to spinning solution by the present invention, and reusing solution jet spinning method is carried out
Spinning；The spin solvent preferably N of the sulfonation non-fluorine hydrocarbon polymer, in N dimethyl acetamide, acetone and chloroform one
Plant or several mixtures, the mass concentration of sulfonation non-fluorine hydrocarbon polymer is preferably 30~40% in the spinning solution, more
Preferably 35~38%.
In the present invention, the solution jet spinning method prepares proton conductive nano fibrofelt and preferably includes following steps：
Sulfonation non-fluorine hydrocarbon polymer and spin solvent are mixed, spinning solution is obtained；
The spinning solution is carried out into jet spinning, proton conductive nano fibrofelt is obtained.
In the present invention, the jet spinning feed liquid speed degree be 3~10ml/h, more preferably 4~8ml/h, most preferably
It is 6ml/h；The attenuating blast pressure of the solution jet spinning is 0.05~0.5MPa；Spinning manifold in the jet spinning
Temperature is preferably 60~95 DEG C, more preferably 70~90 DEG C；Curtain is received in the jet spinning to the reception of spinneret orifice apart from excellent
Elect 40~80cm, more preferably 50~70cm as.
The present invention does not have particular/special requirement to the device of solution jet spinning, is filled using the conventional solution jet spinning in this area
Put.
In some embodiments of the invention, using solution jet spinning device carry out jet spinning preferably include with
Lower step：Using syringe pump by spinning solution through measuring pump feeding spinning head liquid storage tank in, spinning solution extruded shape from spinning head
Into spinning solution thread, spinning solution thread enters spinning manifold after the drawing-off of attenuating blast is refined, and fiber is formed, using blower fan
Fiber is collected and condensed upon on reception lace curtaining, proton conductive nano fibrofelt is obtained；Heated in attenuating blast and spinning manifold
Collective effect under, the solvent in spinning solution thread volatilizees to form fiber.
The present invention prepares substrate nano fibrofelt with thermoplastic resin as raw material using solution jet spinning method.In this hair
In bright, the fusing point of the thermoplastic resin is preferably 160~200 DEG C, more preferably 170~190 DEG C；The thermoplastic resin is excellent
Elect the mixture of one or more in Kynoar, polypropylene and polyester as；Before the substrate nano fibrofelt hot pressing
Thickness is preferably 50~100 μm, more preferably 60~80 μm；The grammes per square metre of the substrate nano fibrofelt is preferably 10~35g/
m2, more preferably 15~25g/m2；The fibre diameter of the substrate nano fibrofelt is preferably 50~800nm, more preferably 100
~600nm, most preferably 200~300nm.In the present invention, the thermoplastic resin has excellent alcohol-rejecting ability, is formed with
The resistance alcohol layer of effect, effectively reduces the methanol permeability of PEM.
In the present invention, the specific method that the use solution jet spinning method prepares substrate nano fibrofelt includes：
Thermoplastic resin and spin solvent are mixed, spinning solution is obtained；
The spinning solution is carried out into jet spinning, proton conductive nano fibrofelt is obtained.
In the present invention, the mass concentration of thermoplastic resin is preferably 18~25% in the spinning solution, more preferably
20~22%；The spin solvent is preferably independently selected from the above-mentioned spin solvent prepared in proton conductive nano fibrofelt,
This is repeated no more；The condition of the jet spinning and specific method with it is above-mentioned prepare it is consistent in proton conductive nano fibrofelt,
This is repeated no more.
The present invention prepares substrate nano fibrofelt and proton conductive nano fibrofelt using solution jet spinning method, using height
Fast air-flow spinning solution thread is carried out it is ultra-fine stretching and make solvent volatilize obtain nanofiber, in spinning manifold inner high speed
The fiber obtained under the turbulent shear effect of air-flow has obvious three-dimensional crimp characteristic and mutually tangles, using this curling
Architectural characteristic makes matrix to be flowed between fiber to obtain more preferable filling effect in hot pressing, and utilizes Nanowire
Tie up the nanofibrous structures that irregular coiled structure constructs permeable membrane, it is to avoid the appearance of film both side surface " transmission barrier layer ".
After obtaining substrate nano fibrofelt and proton conductive nano fibrofelt, the present invention by the substrate nano fibrofelt and
Proton conductive nano fibrofelt spacer stack laying is into sandwich shape nanofiber mats；The substrate nano fibrofelt is sandwich layer, institute
Proton conductive nano fibrofelt is stated for surface layer.In the present invention, the sandwich shape nanofiber mats mesostroma nanofiber mats
Quality is preferably the 10~40% of sandwich shape nanofiber mats gross mass, more preferably 15~35%, most preferably 20~30%；
In some embodiments of the invention, can be according to the grammes per square metre of fibrofelt and thickness control substrate nano fibrofelt and sandwich
The mass ratio of shape nanofiber mats gross mass；In some embodiments of the invention, can also be by controlling substrate nano
The number of plies of fibrofelt or proton conductive nano fibrofelt reaches above-mentioned mass ratio requirement.
After obtaining sandwich shape nanofiber mats, the present invention obtains with cross-film the sandwich shape nanofiber mats hot pressing
It is distributed the PEM of nanofibrous structures.In the present invention, the temperature of the hot pressing is preferably 170~190 DEG C, more preferably
It is 175~185 DEG C；The pressure of the hot pressing is preferably 5~15MPa, more preferably 8~12MPa；The time of the hot pressing is preferred
It is 20~60min, more preferably 30~50min；Hot pressing is carried out present invention preferably uses flat-bed press.
In the present invention, the sandwich shape nanofiber mats preheating that will preferably be obtained before the hot pressing；The temperature of the preheating
Preferably 120~160 DEG C, more preferably 135~155 DEG C；The time of the preheating is preferably 1~8min, more preferably 3~
6min。
After the hot pressing, hot pressing gained composite film heat is preferably quenched into room temperature by the present invention, obtains being received with cross-film distribution
The PEM of rice fibre structure.In the present invention, the thermal quenching is preferably：Hot pressing gained composite membrane is soaked into water
In, it is cooled to room temperature；The thermal quenching water is normal-temperature water, without being cooled down and being lowered the temperature；The present invention is to water used by thermal quenching
Volume there is no particular/special requirement, can by hot pressing gained composite membrane submergence.
The present invention using different polymeric material fusing points difference, (fusing point is to make the relatively low substrate nano fibrofelt of fusing point
160~200 DEG C) melted in hot pressing, (fusing point is more than fully to fill out dystectic proton conductive nano fibrofelt
300 DEG C) fiber gap in, finer and close PEM is obtained, while having three-dimensional crimp characteristic proton conductive nano
Fiber stretches out film surface, obtains being distributed with cross-film the PEM of nanofibrous structures.
The invention provides prepared by preparation method described in a kind of such scheme nanofibrous structures are distributed with cross-film
PEM, including thermoplastic resin matrix layer and the proton conductive nano fiber of cross-film distribution.
In the present invention, the thickness of the PEM with cross-film distribution nanofibrous structures be preferably 40~
120 μm, most preferably more preferably 60~100 μm, 70~90 μm.
With reference to embodiment to the present invention provide with cross-film distribution nanofibrous structures PEM and its
Preparation method is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
With DMF (DMF) as spin solvent, sulfonated polyether sulfone (SPES) is dissolved in spin solvent,
It is prepared into the solution that sulfonated polyether sulfone mass concentration is 35%；Using syringe pump with the speed of 6mL/h by spinning solution through measuring pump
It is fed into spinning head liquid storage tank, spinning solution forms thread when being extruded from spinning head, by high pressure attenuating blast, (pressure is thread
Enter spinning manifold (spin manifold temperature is 90 DEG C) after drawing-off refinement 0.05MPa), in high pressure draught and the common work of spinning manifold
Under, solvent volatilizees to form fiber, is collected on lace curtaining (it is 80cm to receive distance) is received fiber using blower fan, obtains three-dimensional
The sulfonated polyether sulfone nanofiber mats of curling, control the thickness of sulfonated polyether sulfone nanofiber mats for 130 μm, and grammes per square metre is 40g/
m2；
With DMF (DMF) as spin solvent, Kynoar (PVDF) is dissolved in spin solvent,
It is prepared into the solution that Kynoar mass concentration is 20%；Solution jet spinning is carried out using the method in step 1, is gathered
Vinylidene nanofiber mats, thickness is 70 μm, and grammes per square metre is 20g/m2；
Then fibrofelt is entirely built up into " sandwich " fiber layer structure in flat-bed press pressing plate middle berth, wherein PVDF is fine
Dimension felt is placed in " sandwich layer ", and upper and lower two-layer is that SPES fibrofelts (control the quality of PVDF fibrofelts for sandwich shape nanofiber mats are total
Quality 20%), flat-bed press is warmed up to 120 DEG C, by pressing plate and fibrofelt global transfer to flat-bed press, preheating is multiple
Condensating fiber layer 1min, 170 DEG C are warmed up to after preheating carries out hot pressing, hot pressing pressure 5MPa, and hot pressing time is 60min, and hot pressing is completed
Composite membrane is put into normal-temperature water afterwards, thermal quenching to room temperature, there can be cross-film to be distributed the PEM of nanofibrous structures,
Thickness is 120 μm.
It is observed using the surface of many gained PEMs of SEM, observed result is as shown in figure 1, root
According to Fig. 1 as can be seen that gained Surface modification of proton exchange membrane has substantial amounts of nanofiber to be distributed, nanofiber is presented cross-film inside film
Distribution, is formed in a side surface of film to the continuous proton transmitting channel of another side surface.
By the cut-out of gained PEM, section is observed using scanning electron fibrescope, observed result such as Fig. 2 institutes
Show；According to Fig. 2 as can be seen that the matrix that film inside is fully melted is filled, dense non-porous hole shows that the present invention has obtained densification
Complete PEM.
Embodiment 2
With acetone as spin solvent, by the mixture (mixing of sulfonated polyether sulfone (SPES) and sulfonated polyether-ether-ketone (SPEEK)
Mol ratio is 1:1) it is dissolved in spin solvent, is prepared into the solution that SPES and SPEEK total mass concentrations are 33%；Using injection
Through measuring pump be fed into spinning head liquid storage tank spinning solution with the speed of 3mL/h by pump, and spinning solution is formed when being extruded from spinning head
Thread, by entering spinning manifold after the drawing-off refinement of high pressure attenuating blast (pressure is 0.5MPa), (spin manifold temperature is 60 to thread
DEG C), under the collective effect of high pressure draught and spinning manifold, solvent volatilizees to form fiber, collects fiber using blower fan and is connecing
Receive on lace curtaining (it is 60cm to receive distance), obtain the SPES/SPEEK nanofiber mats of three-dimensional crimp, control SPES/SPEEK receives
The thickness of rice fibrofelt is 110 μm, and grammes per square metre is 35g/m2；
With acetone (DMF) as spin solvent, polypropylene is dissolved in spin solvent, being prepared into polypropylene mass concentration is
20% solution；Solution jet spinning is carried out using the method in step 1, polypropylene nano fibrofelt is obtained, thickness is 85 μm,
Grammes per square metre is 30g/m2；
Then fibrofelt is entirely built up into " sandwich " fiber layer structure, wherein polypropylene in flat-bed press pressing plate middle berth
Fibrofelt is placed in " sandwich layer ", and upper and lower two-layer (controls the quality of polypropylene fibre felt for sandwich shape is received for SPES/SPEEK fibrofelts
Rice fibrofelt gross mass 30%), flat-bed press is warmed up to 140 DEG C, pressing plate and fibrofelt global transfer is hot to flat board
Press, preheats composite fibre layer 8min, and 180 DEG C are warmed up to after preheating carries out hot pressing, hot pressing pressure 8MPa, and hot pressing time is
, be put into composite membrane in normal-temperature water after the completion of hot pressing by 45min, and thermal quenching can have cross-film to be distributed nanofiber knot to room temperature
The PEM of structure, thickness is 100 μm.
It is observed using the surface of many gained PEMs of SEM, observed result is as shown in figure 3, root
According to Fig. 3 as can be seen that the nanofiber distribution situation on film surface is similar with embodiment 1；
By the cut-out of gained PEM, section is observed using scanning electron fibrescope, observed result and implementation
Example 1 is similar to.
Embodiment 3
It is with chloroform as spin solvent, the mixture of sulfonate polybenzimidazole (SPBI) and sulfonated polyimide (SPI) is molten
In spin solvent, it is 25% to be prepared into sulfonate polybenzimidazole (SPBI) and sulfonated polyimide (SPI) total mass concentration to solution
Spinning solution；Spinning solution is fed into spinning head liquid storage tank through measuring pump with the speed of 5mL/h using syringe pump, spinning solution from
Spinning head forms thread when extruding, thread after the drawing-off refinement of high pressure attenuating blast (pressure is 0.3MPa) by entering manifold
Body (spin manifold temperature is 75 DEG C), under the collective effect of high pressure draught and spinning manifold, solvent volatilizees to form fiber, using blower fan
Fiber is collected on lace curtaining (it is 50cm to receive distance) is received, the SPBI/SPI nanofiber mats of three-dimensional crimp are obtained, controlled
The thickness of SPBI/SPI nanofiber mats is 80 μm, and grammes per square metre is 25.5g/m2；
With chloroform as spin solvent, polyester is dissolved in spin solvent, be prepared into polyester mass concentration be 20% it is molten
Liquid；Solution jet spinning is carried out using the method in step 1, polypropylene nano fibrofelt is obtained, thickness is 80 μm, and grammes per square metre is
17g/m2；
Then fibrofelt is entirely built up into " sandwich " fiber layer structure in flat-bed press pressing plate middle berth, wherein polyester is fine
Dimension felt is placed in " sandwich layer ", and upper and lower two-layer is that (quality for controlling polyester fiber felt is sandwich shape nanofiber to SPBI/SPI fibrofelts
Felt gross mass 40%), flat-bed press is warmed up to 160 DEG C, by pressing plate and fibrofelt global transfer to flat-bed press, in advance
Hot composite fibre layer 6min, 190 DEG C are warmed up to after preheating carries out hot pressing, hot pressing pressure 10MPa, and hot pressing time is 30min, hot pressing
After the completion of composite membrane is put into normal-temperature water, thermal quenching to room temperature, can have cross-film distribution nanofibrous structures proton hand over
Film is changed, thickness is 60 μm.
It is observed using the surface of many gained PEMs of SEM, observed result is as shown in figure 3, root
According to Fig. 3 as can be seen that the nanofiber distribution situation on film surface is similar with embodiment 1.
By the cut-out of gained PEM, section is observed using scanning electron fibrescope, observed result and implementation
Example 1 is similar to.
Comparative example 1
Sandwich layer is replaced with into sulfonated polyether sulfone nanofiber mats only in laying step, upper and lower two-layer is received for Kynoar
Rice fibrofelt, other conditions are completely and embodiment 1 is identical, obtain compound proton exchange membrane；
Sulfonated polyether sulfone nanofiber mats are placed in sandwich layer, polyvinylidene fluoride nanometer fibrofelt is placed in upper and lower two-layer, heat
Pressure melting after matrix will can play proton conduction sulfonated polyether sulfone nanofiber it is fully wrapped around, in composite film surface two
Side forms " transmission barrier layer ".
Embodiment 4
The contrast that the PEM with cross-film nanofibrous structures that embodiment 1~3 is obtained, comparative example 1 are obtained
PEM and the perfluoro sulfonic acid membrane Nafion117 of in the market purchase carry out performance test, and the data obtained is listed in Table 1 below；
Proton conductivity：Using the measurement of CH1660D types electrochemical workstation and its resistance (inspection of two electrode detection sample films
80 DEG C of testing temperature, humidity 100%), then proton conductivity is calculated by formula 1：
In formula 1, σ：Proton conductivity is represented, unit is (S/cm)；L represents the distance between two electrodes, and unit is cm；t
The thickness of sample film is represented, unit is cm；W represents the width of sample film, and unit is cm, and R represents the resistance of sample film, and unit is
Ω。
Methanol permeability：The methanol permeability of PEM is detected using gas chromatography.
The performance test results of the embodiment 1~3 of table 1, comparative example 1 and perfluoro sulfonic acid membrane Nafion117
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Perfluoro sulfonic acid membrane Nafion117 |
| Proton conductivity (S/cm) | 0.178 | 0.145 | 0.12 | 0.05 | 0.1162 |
| Methanol permeability (cm2s-1) | 1.69×10-8 | 1.22×10-8 | 0.34×10-8 | 0.34×10-8 | 14.1×10-7 |
According to table 1 as can be seen that the PEM proton with cross-film nanofibrous structures that the present invention is provided conducts
Rate is high, and methanol permeability is small, illustrates the presence of the PEM inner transmembrane nanofiber of present invention offer, can be effective
Break the influence of film surface " insulating barrier ", so as to realize the efficient transmission of proton；Testing result according to comparative example understands film table
Face forms transmission barrier layer and can substantially reduce the proton conduction property of film；Perfluoro sulfonic acid membrane Nafion117 proton conductivities are less than
The PEM that the present invention is obtained, and its methanol permeability is very high, alcohol-rejecting ability is poor, obtained by the present invention with cross-film nanometer
The performance of the PEM of fibre structure is substantially better than comparative example and perfluoro sulfonic acid membrane Nafion117.
As seen from the above embodiment, the proton with cross-film nanofibrous structures prepared by the preparation method that the present invention is provided
Exchange membrane excellent performance, can effectively break the influence of film surface " transmission barrier layer ", improve proton transfer efficiency；And this hair
The preparation method of bright offer is simple, have developed using the new method of the volume than PEM of pressure sintering, greatly reduces matter
The preparation cost of proton exchange.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. it is a kind of with cross-film distribution nanofibrous structures PEM preparation method, it is characterised in that including following
Step：
With sulfonation non-fluorine hydrocarbon polymer as raw material, proton conductive nano fibrofelt is prepared using solution jet spinning method；
With thermoplastic resin as raw material, substrate nano fibrofelt is prepared using solution jet spinning method；
The substrate nano fibrofelt and proton conductive nano fibrofelt wall lay-up are built up into sandwich shape nanofiber mats；Institute
Substrate nano fibrofelt is stated for sandwich layer, the proton conductive nano fibrofelt is surface layer；
By the sandwich shape nanofiber mats hot pressing, obtain being distributed with cross-film the PEM of nanofibrous structures.
2. preparation method according to claim 1, it is characterised in that the sulfonation non-fluorine hydrocarbon polymer is sulfonated polyether
The mixture of one or more in sulfone, sulfonated polyether-ether-ketone, sulfonate polybenzimidazole and sulfonated polyimide.
3. preparation method according to claim 1, it is characterised in that the thermoplastic resin is Kynoar, poly- third
The mixture of one or more in alkene and polyester.
4. the preparation method according to claims 1 to 3 any one, it is characterised in that the proton conductive nano fiber
Thickness before felt hot pressing is 50~150 μm；Thickness before the substrate nano fibrofelt hot pressing is 50~100 μm.
5. preparation method according to claim 1, it is characterised in that the sandwich shape nanofiber mats mesostroma Nanowire
The quality for tieing up felt is the 10~40% of sandwich shape nanofiber mats gross mass.
6. preparation method according to claim 1, it is characterised in that the temperature of the hot pressing is 170~190 DEG C；It is described
The pressure of hot pressing is 5~15MPa；The time of the hot pressing is 20~60min.
7. the preparation method according to claim 1,4 or 6, it is characterised in that also include preheating before the hot pressing；It is described pre-
The temperature of heat is 120~160 DEG C；The time of the preheating is 1~8min.
8. the proton with cross-film distribution nanofibrous structures that prepared by preparation method described in claim 1~7 any one is handed over
Change film, including thermoplastic resin matrix layer and the proton conductive nano fiber of cross-film distribution.
9. PEM according to claim 8, it is characterised in that the thickness of the PEM is 40~120 μ
m。
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| CN113270622A (en) * | 2021-04-28 | 2021-08-17 | 中国石油大学(北京) | Polymer-based double-layer nanofiber composite proton exchange membrane and preparation method thereof |
| CN114614059A (en) * | 2022-03-21 | 2022-06-10 | 中国石油大学(北京) | Modified nanofiber composite proton exchange membrane and preparation method and application thereof |
| CN114703559A (en) * | 2022-04-22 | 2022-07-05 | 上海水星家用纺织品股份有限公司 | Preparation method and application of nanofiber spinning solution |
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| CN114614059A (en) * | 2022-03-21 | 2022-06-10 | 中国石油大学(北京) | Modified nanofiber composite proton exchange membrane and preparation method and application thereof |
| CN114703559A (en) * | 2022-04-22 | 2022-07-05 | 上海水星家用纺织品股份有限公司 | Preparation method and application of nanofiber spinning solution |
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