CN113903962A - Preparation method of dyed viscose cellulose proton exchange membrane for fuel cell - Google Patents
Preparation method of dyed viscose cellulose proton exchange membrane for fuel cell Download PDFInfo
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- CN113903962A CN113903962A CN202111085239.XA CN202111085239A CN113903962A CN 113903962 A CN113903962 A CN 113903962A CN 202111085239 A CN202111085239 A CN 202111085239A CN 113903962 A CN113903962 A CN 113903962A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 238000001816 cooling Methods 0.000 claims abstract description 17
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- 238000012986 modification Methods 0.000 claims description 9
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- 238000005096 rolling process Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- HMHFERXOZSZRML-UHFFFAOYSA-M trimethyl-(3-methyloxiran-2-yl)azanium;chloride Chemical compound [Cl-].CC1OC1[N+](C)(C)C HMHFERXOZSZRML-UHFFFAOYSA-M 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
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- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a preparation method of a dyed viscose cellulose proton exchange membrane for a fuel cell, which comprises the following steps of stretching a viscose fiber membrane, modifying 2, 3-epoxypropyl trimethyl ammonium chloride cations, and dyeing the cation-modified viscose fiber membrane material by using an X-2R type active dye: weighing 1-4 owf% of X-2R type reactive dye to prepare a dye solution, putting the obtained viscose fiber membrane into the dye solution, dyeing at room temperature, slowly heating, adding sodium carbonate for fixation treatment, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose color, and naturally drying. The dyed viscose cellulose proton exchange membrane prepared by the invention has good comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of preparation of proton exchange membranes for fuel cells, and particularly relates to a preparation method of a dyed viscose cellulose proton exchange membrane for a fuel cell.
Background
In order to realize sustainable development, the demand of human beings for clean energy is increasing, so that a Proton Exchange Membrane Fuel Cell (PEMFC) is attracting the attention of many researchers as a clean and efficient device capable of converting chemical energy into electric energy. As a core element of PEMFCs, the superiority and inferiority of Proton Exchange Membrane (PEM) performance may determine the performance, cost, and even lifetime of PEMFCs. The current commercial proton exchange membrane used at home and abroad is composed of a perfluorinated polymer main chain and sulfonic acid side chains, and is most typically manufactured by DuPont in the United states in the beginning of the 19 th century and the 80 th century
A series of films are provided,
membranes rapidly develop and become a measure of proton exchange membrane performance due to their excellent conductivity combined with a good balance of properties. To date, except
In addition to the series of membranes, there have been developed
Series of membranes, Dow membranes,
Series of films, and the like.
However, Nafion membranes still suffer from the following 3 drawbacks: firstly, the material is easy to degrade at high temperature; secondly, the synthesis process is complex, the technology is difficult, the cost is high, and the price of the finished product is high; and thirdly, the fuel permeability is high, and methanol is easy to permeate when the fuel is used for a methanol fuel cell. The development of new ideal proton exchange membranes to replace Nafion membranes has become a popular area of research. Among many candidate materials, cellulose (Cell) and its derived materials are receiving attention from researchers because of their own advantages such as high mechanical strength, thermal stability, bio-affinity, high electrochemical stability, natural carbonaceous characteristics, easy modification, and abundant surface active functional groups. The viscose belongs to a regenerated cellulose, the stock solution of which is natural fiber as a raw material, is made into soluble cellulose xanthate through the procedures of alkalization, aging, sulfonation and the like, and the macromolecular structure of the cellulose xanthate not only has anion groups capable of conducting protons, but also has a large number of reactive groups capable of introducing more ion conducting groups, and has good film-forming property, so the cellulose xanthate can be used for preparing ion exchange membranes.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The invention provides a preparation method of a dyed viscose cellulose proton exchange membrane for a fuel cell, which comprises the following steps,
(1) stretching the viscose fiber film: pouring the viscose stock solution into a polytetrafluoroethylene mold, immersing the polytetrafluoroethylene mold into a coagulating bath at 40-55 ℃, placing the viscose fiber film into warm water after the viscose fiber film is preliminarily formed, stretching the viscose fiber film, immersing the stretched viscose fiber film into the coagulating bath, washing, plasticizing, washing and freeze-drying;
(2)2, 3-epoxypropyltrimethylammonium chloride cation modification: soaking the viscose fiber film obtained in the step (1) in a NaOH solution, soaking the soaked viscose fiber film into the 2, 3-epoxypropyltrimethylammonium chloride solution, then carrying out two-soaking and two-rolling, baking the viscose fiber film in an oven, and naturally drying after cooling;
(3) dyeing the cationic modified viscose fiber membrane material by using X-2R type reactive dye: weighing 1-4 owf% of X-2R type reactive dye to prepare a dye solution, putting the viscose fiber membrane obtained in the step (2) into the dye solution, dyeing at room temperature, slowly heating, adding sodium carbonate for fixation, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose color, and naturally drying.
The preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: pouring a viscose stock solution into a polytetrafluoroethylene mold, immersing the viscose stock solution into a 50 ℃ coagulating bath, preliminarily forming a viscose fiber membrane within 10-15 seconds, placing the viscose fiber membrane into 50 ℃ warm water, directionally stretching the viscose fiber membrane, immersing the stretched viscose fiber membrane into the coagulating bath for full coagulation, repeatedly washing the viscose fiber membrane with deionized water for several times, putting the viscose fiber membrane into a 30-40% glycerol solution for plasticizing for 4-6 hours, washing the viscose fiber membrane with the deionized water, and then placing the viscose fiber membrane into a freeze dryer for freeze drying for 12 hours at-40 ℃.
The preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: the oriented stretch viscose fiber membrane is stretched to 1.5 times of the original length by clamping two ends of the membrane along the length direction by using tweezers.
The preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: and (2) soaking the viscose fiber membrane obtained in the step (1) in a 2-3 wt% NaOH solution for 30-40 min, preparing a 40-45 g/L2, 3-epoxypropyltrimethylammonium chloride solution, soaking the soaked viscose fiber membrane in the 2, 3-epoxypropyltrimethylammonium chloride solution for 30-40 min, then carrying out double-soaking and double-rolling, baking the viscose fiber membrane in an oven at 110-120 ℃ for 3-4 min, and naturally cooling.
The preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: weighing 1-4 owf% of X-2R type reactive dye to prepare dye liquor, wherein the weight ratio of the dye liquor to the bath is 1: 40-50 putting the viscose fiber membrane obtained in the step (2) into the dye liquor, dyeing for 30-40 min at room temperature, putting the beaker into a constant-temperature water bath, slowly heating to 50-60 ℃, adding sodium carbonate for color fixing treatment, wherein the concentration of the sodium carbonate is 10-15 g/L, taking out the beaker after 30-40 min, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose colors, and naturally airing and storing for later use.
The preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: in the step (3), 3 owf% of X-2R type reactive dye is weighed to prepare dye liquor.
The preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: in the step (3), the molecular structural formula of the 3 owf% X-2R type reactive dye is shown as the following formula,
the preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: the thickness of the dyed cellulose proton exchange membrane for the fuel cell is 100-150 mu m.
The preparation method of the dyed cellulose proton exchange membrane for the fuel cell is a preferable scheme: the coagulation bath has a composition of 118g/L H2SO4、320g/L Na2SO4And 11g/L ZnSO4。
The invention has the beneficial effects that: the viscose fiber film is prepared by coagulating bath wet film forming. The orientation degree of macromolecular chains in the film material is improved by utilizing a manual stretching method, so that the mechanical property of the film material is improved. The glycerol is used as a plasticizer to cut into macromolecular chains so as to improve the flexibility of the film material. The low-temperature freeze drying method is used for removing water, so that the phenomenon of large-degree shrinkage of the membrane material in the natural drying process is effectively avoided. The prepared membrane material is modified by 2, 3-epoxypropyl trimethyl ammonium chloride cation modifier (dye uptake percentage can be greatly increased, number of conductive units can be increased), and then is dyed by X-2R type active dye to prepare the dyed viscose cellulose proton exchange membrane, and experimental results show that the prepared dyed viscose cellulose proton exchange membrane has a compact structure, good mechanical properties and Cell/3 DEGThe tensile strength of the wf% X-2R viscose cellulose film is 54MPa, the elongation at break reaches 62%, the thermal stability is good, the proton conductivity of the dyed cellulose film is obviously increased, and the Cell/3 owf% X-2R viscose cellulose film reaches 3.88 multiplied by 10-3S·cm-1. In conclusion, the dyed viscose cellulose proton exchange membrane prepared by the method shows good comprehensive performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a scanning electron micrograph (4000X) of a cross-section of (a) an unstained viscose cellulose membrane and (b) a dyed viscose cellulose proton exchange membrane (3 owf%).
FIG. 2 is a stress-strain curve of a series of viscose cellulose films.
FIG. 3 is a thermogravimetric plot of Cell/3 owf% X-2R stained viscose cellulose films.
FIG. 4 is a graph of the proton conductivity (25 ℃) of a series of dyed viscose cellulose films.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Reagents and instrumentation:
stock viscose, industrial goods, funing australian science and technology, llc; glycerol (AR), chengdu lacoda chemical agents limited; sodium carbonate (AR), jiangsu chemical agents ltd; sodium chloride (AR), chemical agents ltd of the national drug group; 2, 3-epoxypropyltrimethylammonium chloride (AR), national drug group chemicals ltd; sodium hydroxide (AR), chemical agents ltd of the national drug group; sulfuric Acid (AR), national drug group chemical agents limited; X-2R type, KN-R reactive dyes, technical products, Wujiang peach garden dyes, Inc.; cellulose crystallites (AR), gudooka chemical agents limited; urea (AR), chemical agents ltd of the national drug group.
Universal testing machine (model H5K-S), Hounsfield, UK; electrochemical workstation (model CHI 660E), shanghai chenhua instruments ltd; TG-DSC synchronous thermal analyzer (model STA 449C), German Steed instruments manufacturing Ltd; field emission scanning electron microscope (7593-H type), Hitachi, Japan; precision electronic balance (MP200A model), shanghai shangyouming scientific instruments ltd; magnetic stirrers (model 85-2A), manufactured by Jinan Oolabo technologies, Inc.; vacuum drying oven (DX-ZKX100 type), Henno Lixing science and technology Co., Ltd, Beijing; low temperature reactor (DLSB-100), Shanghai Baoling instruments and Equipment Co., Ltd; germany Eppendorf Centrifuge (Centrifuge model 5702).
Example 1:
preparation of regenerated cellulose membrane control (self-made in laboratory): preparing a regenerated cellulose membrane by adopting a low-temperature NaOH/urea method, preparing 250mL of aqueous solvent (8 wt% of sodium hydroxide and 12 wt% of urea), placing the aqueous solvent in a low-temperature reactor (-12.6 ℃), placing 5g of cellulose microcrystal in the aqueous solvent, stirring the aqueous solvent at 6000rpm for 10 minutes, centrifugally separating the aqueous solvent at 8000rpm for 5 minutes, pouring a clear liquid part into a polytetrafluoroethylene mold (the thickness is 0.5mm), and naturally drying the clear liquid part to form a membrane. The conductivity of the product was 4.47X 10 by AC impedance measurement-5S·cm-1A breaking strength of 14MPa, fractureThe elongation was 1%.
Preparing a dyed viscose cellulose proton exchange membrane:
preparing a coagulating bath: the composition of the coagulation bath was 118g/L H2SO4、320g/L Na2SO4And 11g/L ZnSO4The specific gravity of the coagulation bath is 1.32, 59g H2SO4、160g Na2SO4And 5.5g of ZnSO4The resulting solution was added to 435.5mL of deionized water to prepare 500mL of a coagulation bath.
(1) Stretching the viscose fiber film: pouring the viscose stock solution into a polytetrafluoroethylene mold (the thickness is 0.5mm, the length is 10cm, and the width is 3cm), immersing the polytetrafluoroethylene mold into a coagulating bath at 50 ℃, preliminarily forming the viscose fiber membrane within about 10 seconds, placing the viscose fiber membrane into warm water at 50 ℃, slowly and directionally stretching the two ends of the membrane to 15cm by using tweezers on the premise of ensuring the width of the membrane to be unchanged as much as possible so as to improve the arrangement direction of macromolecular chains of the viscose fiber membrane, immersing the stretched viscose fiber membrane into the coagulating bath for full coagulation, repeatedly washing the viscose fiber membrane by using deionized water for several times, putting the viscose fiber membrane into a glycerol solution with the mass fraction (g: mL) of 30 percent for plasticizing for 4 hours, repeatedly washing the viscose fiber membrane by using the deionized water for several times, then placing the viscose fiber membrane into a freeze dryer for freeze drying for 12 hours at the temperature of minus 40 ℃, and taking out for later use.
(2)2, 3-epoxypropyltrimethylammonium chloride cation modification: soaking the viscose fiber membrane obtained in the step (1) in a 2 wt% NaOH solution for 30min to prepare 250mL of a 40 g/L2, 3-epoxypropyltrimethylammonium chloride solution, soaking the soaked viscose fiber membrane in the 2, 3-epoxypropyltrimethylammonium chloride solution for 30min, then carrying out double-soaking and double-rolling, baking the viscose fiber membrane in an oven at 120 ℃ for 3min, and naturally cooling.
(3) Dyeing the cationic modified viscose fiber membrane material by using X-2R type reactive dye: weighing dyes (1 owf%, 2 owf%, 3 owf% and 4 owf%) with different concentrations to prepare dye liquor, wherein the dye liquor is prepared according to a bath ratio of 1: 50, placing the viscose fiber membrane obtained in the step (2) into the dye solution, dyeing for 30min at room temperature, placing a beaker into a constant-temperature water bath, slowly heating to 60 ℃, adding sodium carbonate for color fixation treatment, wherein the concentration of the sodium carbonate is 10g/L, taking out the beaker after 30min, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose color, naturally drying and storing for later use, wherein the thickness of the viscose fiber membrane is 100-micron and 120 microns.
And (3) morphology characterization:
the viscose fiber film is brittle-broken by liquid nitrogen, and the section appearance of the film is represented by a field emission scanning electron microscope (Hitachi, Japan, model 7593-H).
And (3) testing mechanical properties:
the test was carried out using a universal tester (Hounsfield, UK, model H5K-S) at a tensile rate of 10mm/min, and the specimens were cut into specimens having a length of 5cm and a width of 1 cm. Three samples were tested to ensure test accuracy.
Thermal stability performance:
the thermal stability of the film was measured by a TG-DSC synchronous thermal analyzer (model STA449C, manufactured by Steed instruments Ltd., Germany) under nitrogen, and the temperature was raised to 750 ℃ at a rate of 10 ℃/min.
Proton conductivity test:
proton conductivity was measured by ac impedance method: a sample with the size of 1cm multiplied by 1cm is cut, soaked in 1mol/L sulfuric acid solution for 24 hours and washed to be neutral by deionized water. The test was carried out by an alternating current impedance method using an electrochemical workstation (CHI660E, Shanghai Chenghua instruments, Ltd.), and the test frequency was 1 to 1 MHz. The proton conductivity σ is obtained by calculation using the following formula:
σ＝d/RS
wherein: σ is proton conductivity (S · cm)-1) (ii) a d is the thickness (cm) of the film material; r is the resistance (omega) of the film material; s is the contact area (cm) of the electrode and the membrane material2)。
The experimental results are as follows:
FIG. 1 is a scanning electron microscope image of 4000-fold magnification of cross-sections of an undyed viscose cellulose film and a dyed viscose cellulose proton exchange membrane (3 owf%) according to the present invention. As can be seen from the figure, the section of the undyed viscose cellulose membrane is rough, the membrane becomes smooth after being modified by the cationic modifier and the dye, hydrogen bond bridging, dynamic crosslinking and chemical bonding are formed between cellulose molecules due to the reaction of modifier molecules and dye molecules with fibers, and the multiple water immersion treatment is also favorable for removing incompatible particulate matters in the membrane. The section of the film shows a compact structure, which shows that the film forming performance of the viscose fiber is better in the process of regeneration in the coagulating bath, and the stretching operation effectively promotes the directional arrangement of macromolecular chains. In addition, the cationic modifier and the dye do not agglomerate, which is also beneficial to improving the mechanical property and proton conductivity of the membrane.
Mechanical properties: in practical applications, proton exchange membranes require sufficient mechanical strength to operate for long periods of time. FIG. 2 is a graph of mechanical tensile properties of a series of viscose cellulose proton exchange membranes of the present invention. PCE is a self-made regenerated cellulose film, PSR is an undyed unstretched un-stretched un-plasticized viscose cellulose film, PSRST is an undyed stretched and plasticized viscose cellulose film, DSRT is a dyed (3 owf%) and stretched viscose cellulose film, and DSRST is a dyed (3 owf%) and plasticized viscose cellulose film prepared in example 1. As can be seen from the figure, the mechanical properties of the PCE are the worst, and probably the PCE has the defects that the content of salt substances in the PCE is high during the formation of the film, charged groups are lacking in macromolecules, the PCE is difficult to form reliable combination with the salt substances, and a large amount of urea and caustic soda are lost in the later washing process, so that the pores in the PCE are too large. The PSR has breaking strength of 32MPa and breaking elongation of 16%, and is mainly because the compatibility of each component in the viscose is good, and the charged groups in the macromolecular memory can effectively retain effective components. The PSRST breaking strength is 43Mpa, the breaking elongation is 36%, which shows that the mechanical property of the film material is obviously improved through stretching and plasticizing treatment. The DSRT breaking strength is 48Mpa, the breaking elongation is 17%, mainly because the mutual connection of all components in the film is enhanced along with the increase of the concentration of the active dye, the ionic group of the viscose cellulose, the quaternary ammonium functional group in the cation modifier and the sulfonic acid group in the dye form an ionic bond, the sulfonic acid group and the hydroxyl in the cellulose form a hydrogen bond network, the mechanical property of the film is enhanced, the ionic bond and the hydrogen bond have stronger action when the concentration of the dye is higher, and therefore, the breaking strength is improved. Meanwhile, because no plasticizing treatment is carried out, the macromolecular chains of the membrane material are too tightly connected, so that slippage is difficult, and the elongation at break is reduced. The DSRST film prepared in example 1 had a breaking strength of 54MPa and an elongation at break of 62%. The glycerol weakens the tightness of the action between macromolecular chains on one hand, strengthens the hydrogen bond action in the film on the other hand, forms a dynamic crosslinking mode and effectively improves the mechanical property. The results show that the mechanical properties of a series of dyed membranes are improved, and the membranes can be used in fuel cells.
Thermal stability performance: proton exchange membranes require good thermal stability. FIG. 3 is a thermogravimetric plot of a Cell/3 owf% X-2R viscose cellulose film of the present invention. The degradation of the membrane material can be divided into three stages, the first stage below 150 ℃ being attributable to the evaporation of water. There was little mass loss from 150 ℃ to 250 ℃, and weight loss at this stage at 250 ℃ to 280 ℃ was associated with degradation of the dye and cationic modifier. The third stage at 280 ℃ or higher is a pyrolysis stage of cellulose, and the mass retention rate at 750 ℃ is 16%. The result shows that the dyed cellulose proton exchange membrane has good thermal stability below 280 ℃ and can meet the requirements of low-temperature fuel cells.
Proton conductivity: and measuring the impedance of the membrane material by using an alternating current impedance method by using an electrochemical workstation, and calculating the conductivity of the membrane material. FIG. 4 is the proton conductivity of the dyed viscose cellulose film of the present invention, and it can be seen that the conductivity of the undyed viscose cellulose film is only 3.68X 10 at 25 deg.C-4S·cm-1. After dyeing, the conductivity of the membrane is improved by one order of magnitude, and the proton conductivity of the membrane is increased along with the increase of the dye dosage. The proton conductivities of the cellulose membranes of Cell/1 owf% X-2R, Cell/2 owf% X-2R, Cell/3 owf% X-2R, Cell/4 owf% X-2R were 1.71X 10, respectively-3S·cm-1、2.69×10-3S·cm-1、3.88×10-3S·cm-1、3.81×10-3S·cm-1The proton conductivity of Cell/3 owf% X-2R viscose cellulose film is highest. This is because the reactive dye X-2R contains sulfonic acid groups, which can provide proton channels for the membrane. In addition, the hydrophilic sulfonic acid group can absorb more water as a proton carrier, thereby improving proton conductivity. While the proton conductivity of the Cell/4 owf% X-2R cellulose film was slightly decreased, indicating thatThe dye uptake of the viscose film reaches a peak value, no more sulfonic acid groups can be introduced, and the agglomeration of dye molecules hinders the conduction of protons, thereby causing the reduction of proton conductivity.
The viscose is stretched in a coagulating bath to prepare a viscose fiber membrane, the viscose fiber membrane is modified by a 2, 3-epoxypropyltrimethylammonium chloride cation modifier and then dyed by X-2R type reactive dye to prepare the dyed viscose cellulose proton exchange membrane, and experimental results show that the prepared dyed viscose cellulose proton exchange membrane has a compact structure and good mechanical property, the tensile strength of a Cell/3 owf% X-2R cellulose membrane is 54MPa, the elongation at break is 62%, the thermal stability is good, the proton conductivity of the dyed viscose cellulose membrane is increased by 10 times, and the Cell/3 owf% X-2R cellulose membrane reaches 3.88 multiplied by 10- 3S·cm-1. In conclusion, the dyed viscose cellulose proton exchange membrane prepared by the method shows good comprehensive performance.
Comparative example 1:
preparing a dyed viscose cellulose proton exchange membrane:
preparing a coagulating bath: the composition of the coagulation bath was 118g/L H2SO4、320g/L Na2SO4And 11g/L ZnSO4The specific gravity of the coagulation bath is 1.32, 59g H2SO4、160g Na2SO4And 5.5g of ZnSO4The resulting solution was added to 435.5mL of deionized water to prepare 500mL of a coagulation bath.
(1) Stretching the viscose fiber film: pouring the viscose stock solution into a polytetrafluoroethylene mold (the thickness is 0.5mm, the length is 10cm, and the width is 3cm), immersing the polytetrafluoroethylene mold into a coagulating bath at 50 ℃, preliminarily forming the viscose fiber membrane within about 10 seconds, placing the viscose fiber membrane into warm water at 50 ℃, slowly and directionally stretching the two ends of the membrane to 15cm by using tweezers on the premise of ensuring the width of the membrane to be unchanged as much as possible so as to improve the arrangement direction of macromolecular chains of the viscose fiber membrane, immersing the stretched viscose fiber membrane into the coagulating bath for full coagulation, repeatedly washing the viscose fiber membrane by using deionized water for several times, putting the viscose fiber membrane into a glycerol solution with the mass fraction (g: mL) of 30 percent for plasticizing for 4 hours, repeatedly washing the viscose fiber membrane by using the deionized water for several times, then placing the viscose fiber membrane into a freeze dryer for freeze drying for 12 hours at the temperature of minus 40 ℃, and taking out for later use.
(2)2, 3-epoxypropyltrimethylammonium chloride cation modification: soaking the viscose fiber membrane obtained in the step (1) in a 2 wt% NaOH solution for 30min to prepare 250mL of 0g/L and 20 g/L2, 3-epoxypropyltrimethylammonium chloride solution, soaking the soaked viscose fiber membrane in the 2, 3-epoxypropyltrimethylammonium chloride solution for 30min, then carrying out double-soaking and double-rolling, baking the viscose fiber membrane in an oven at 120 ℃ for 3min, and naturally cooling.
(3) Dyeing the cationic modified viscose fiber membrane material by using X-2R type reactive dye: weighing 3 owf% to prepare dye liquor, and mixing the dye liquor according to a bath ratio of 1: 50, placing the viscose fiber membrane obtained in the step (2) into the dye solution, dyeing for 30min at room temperature, placing a beaker into a constant-temperature water bath, slowly heating to 60 ℃, adding sodium carbonate for color fixation treatment, wherein the concentration of the sodium carbonate is 10g/L, taking out the beaker after 30min, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose color, naturally drying and storing for later use, wherein the thickness of the viscose fiber membrane is 100-micron and 120 microns.
And (3) performance test results:
membrane material with 0g/L cationic modifier (i.e. no cationization modification): the conductivity of the product was 1.38X 10 by AC impedance measurement-3S·cm-1The breaking strength was 43MPa and the elongation at break was 35%.
Membrane material with 20g/L cationic modifier (i.e. not modified): the conductivity of the product was 2.14X 10 by AC impedance measurement-3S·cm-1The breaking strength was 39MPa and the elongation at break was 29%.
Comparative example 2:
preparing a dyed viscose cellulose proton exchange membrane:
preparing a coagulating bath: the composition of the coagulation bath was 118g/L H2SO4、320g/L Na2SO4And 11g/L ZnSO4The specific gravity of the coagulation bath is 1.32, 59g H2SO4、160g Na2SO4And 5.5g of ZnSO4The resulting solution was added to 435.5mL of deionized water to prepare 500mL of a coagulation bath.
(1) Stretching the viscose fiber film: pouring the viscose stock solution into a polytetrafluoroethylene mold (the thickness is 0.5mm, the length is 10cm, and the width is 3cm), immersing the polytetrafluoroethylene mold into a coagulating bath at 50 ℃, preliminarily forming the viscose fiber membrane within about 10 seconds, placing the viscose fiber membrane into warm water at 50 ℃, slowly and directionally stretching the two ends of the membrane to 15cm by using tweezers on the premise of ensuring the width of the membrane to be unchanged as much as possible so as to improve the arrangement direction of macromolecular chains of the viscose fiber membrane, immersing the stretched viscose fiber membrane into the coagulating bath for full coagulation, repeatedly washing the viscose fiber membrane by using deionized water for several times, putting the viscose fiber membrane into a glycerol solution with the mass fraction (g: mL) of 30 percent for plasticizing for 4 hours, repeatedly washing the viscose fiber membrane by using the deionized water for several times, then placing the viscose fiber membrane into a freeze dryer for freeze drying for 12 hours at the temperature of minus 40 ℃, and taking out for later use.
(2)2, 3-epoxypropyltrimethylammonium chloride cation modification: soaking the viscose fiber membrane obtained in the step (1) in a 2 wt% NaOH solution for 30min to prepare 250mL of a 40 g/L2, 3-epoxypropyltrimethylammonium chloride solution, soaking the soaked viscose fiber membrane in the 2, 3-epoxypropyltrimethylammonium chloride solution for 30min, then carrying out double-soaking and double-rolling, baking the viscose fiber membrane in an oven at 120 ℃ for 3min, and naturally cooling.
(3) Dyeing the cationic modified viscose fiber membrane material by using X-2R type reactive dye: weighing 3 owf% to prepare dye liquor, and mixing the dye liquor according to a bath ratio of 1: 50, placing the viscose fiber membrane obtained in the step (2) into the dye solution, dyeing for 30min at room temperature, placing a beaker into a constant-temperature water bath, slowly heating to 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃, adding sodium carbonate for color fixing treatment, wherein the concentration of the sodium carbonate is 10g/L, taking out the beaker after 30min, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping and deionized water, washing off loose colors, naturally airing and storing for later use, wherein the thickness of the viscose fiber membrane is 100-120 mu m.
And (3) performance test results:
the conductivity of the series membrane materials is 2.11 multiplied by 10 measured by an alternating current impedance method-3S·cm-1(40℃)、2.39×10-3S·cm-1(50℃)、3.88×10-3S·cm-1(60℃)、3.91×10-3S·cm-1(70℃)、3.35×10-3S·cm-1(80 ℃ C.). The temperature is too low, the color fixing degree is low, dye loss is obvious after multiple times of washing, and the number of conductive units in the film is relatively low; at too high a temperature, there is a more pronounced hydrolysis of the already bound dye, which also results in a reduction in the number of conductive elements in the film.
Comparative example 3:
preparing a dyed viscose cellulose proton exchange membrane:
preparing a coagulating bath: the composition of the coagulation bath was 118g/L H2SO4、320g/L Na2SO4And 11g/L ZnSO4The specific gravity of the coagulation bath is 1.32, 59g H2SO4、160g Na2SO4And 5.5g of ZnSO4The resulting solution was added to 435.5mL of deionized water to prepare 500mL of a coagulation bath.
(1) Stretching the viscose fiber film: pouring the viscose stock solution into a polytetrafluoroethylene mold (the thickness is 0.5mm, the length is 10cm, and the width is 3cm), immersing the polytetrafluoroethylene mold into a coagulating bath at 50 ℃, preliminarily forming the viscose fiber membrane within about 10 seconds, placing the viscose fiber membrane into warm water at 50 ℃, slowly and directionally stretching the two ends of the membrane to 15cm by using tweezers on the premise of ensuring the width of the membrane to be unchanged as much as possible so as to improve the arrangement direction of macromolecular chains of the viscose fiber membrane, immersing the stretched viscose fiber membrane into the coagulating bath for full coagulation, repeatedly washing the viscose fiber membrane by using deionized water for several times, putting the viscose fiber membrane into a glycerol solution with the mass fraction (g: mL) of 30 percent for plasticizing for 4 hours, repeatedly washing the viscose fiber membrane by using the deionized water for several times, then placing the viscose fiber membrane into a freeze dryer for freeze drying for 12 hours at the temperature of minus 40 ℃, and taking out for later use.
(2)2, 3-epoxypropyltrimethylammonium chloride cation modification: soaking the viscose fiber membrane obtained in the step (1) in a 2 wt% NaOH solution for 30min to prepare 250mL of a 40 g/L2, 3-epoxypropyltrimethylammonium chloride solution, soaking the soaked viscose fiber membrane in the 2, 3-epoxypropyltrimethylammonium chloride solution for 30min, then carrying out double-soaking and double-rolling, baking the viscose fiber membrane in an oven at 120 ℃ for 3min, and naturally cooling.
(3) Dyeing the cationic modified viscose fiber membrane material by using KN-R type reactive dye: weighing 3 owf% to prepare dye liquor, and mixing the dye liquor according to a bath ratio of 1: 50 placing the viscose fiber membrane obtained in the step (2) into the dye solution, dyeing for 30min at 60 ℃ in a constant-temperature water bath, slowly heating to 80 ℃, adding sodium carbonate for color fixing treatment, wherein the concentration of the sodium carbonate is 10g/L, taking out the beaker after 30min, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose colors, naturally drying and storing for later use, wherein the thickness of the viscose fiber membrane is 100-120 mu m.
And (3) performance test results:
the conductivity of the series membrane materials measured by an alternating current impedance method is 8.52 multiplied by 10-4S·cm-1. The KN-R type reactive dye is an anthraquinone vinyl sulfone type dye, the reaction capability of the KN-R type reactive dye with cellulose is not as good as that of an X type dye, the possibility of hydrolysis is high due to the fact that the fixation temperature is higher, in addition, only one sulfonic acid group which can be used for conducting electricity is arranged in the molecular structure of the KN-R type reactive dye, the actual content of the dye in a membrane after the KN-R type reactive dye is washed and soaked for many times is lower, and the conductivity of the KN-R type reactive dye is lower.
Chemical structure of KN-R type reactive dye:
it should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a dyed viscose cellulose proton exchange membrane for a fuel cell is characterized by comprising the following steps: the method comprises the following steps of (1),
(1) stretching the viscose fiber film: pouring the viscose stock solution into a polytetrafluoroethylene mold, immersing the polytetrafluoroethylene mold into a coagulating bath at 40-55 ℃, placing the viscose fiber film into warm water after the viscose fiber film is preliminarily formed, stretching the viscose fiber film, immersing the stretched viscose fiber film into the coagulating bath, washing, plasticizing, washing and freeze-drying;
(2)2, 3-epoxypropyltrimethylammonium chloride cation modification: soaking the viscose fiber film obtained in the step (1) in a NaOH solution, soaking the soaked viscose fiber film into the 2, 3-epoxypropyltrimethylammonium chloride solution, then carrying out two-soaking and two-rolling, baking the viscose fiber film in an oven, and naturally drying after cooling;
(3) dyeing the cationic modified viscose fiber membrane material by using X-2R type reactive dye: weighing 1-4 owf% of X-2R type reactive dye to prepare a dye solution, putting the viscose fiber membrane obtained in the step (2) into the dye solution, dyeing at room temperature, slowly heating, adding sodium carbonate for fixation, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose color, and naturally drying.
2. The method of preparing a dyed cellulose proton exchange membrane for a fuel cell according to claim 1, wherein: pouring a viscose stock solution into a polytetrafluoroethylene mold, immersing the viscose stock solution into a 50 ℃ coagulating bath, preliminarily forming a viscose fiber membrane within 10-15 seconds, placing the viscose fiber membrane into 50 ℃ warm water, directionally stretching the viscose fiber membrane, immersing the stretched viscose fiber membrane into the coagulating bath for full coagulation, repeatedly washing the viscose fiber membrane with deionized water for several times, putting the viscose fiber membrane into a 30-40% glycerol solution for plasticizing for 4-6 hours, washing the viscose fiber membrane with the deionized water, and then placing the viscose fiber membrane into a freeze dryer for freeze drying for 12 hours at-40 ℃.
3. The method of preparing a dyed cellulose proton exchange membrane for a fuel cell according to claim 1 or 2, characterized in that: the oriented stretch viscose fiber membrane is stretched to 1.5 times of the original length by clamping two ends of the membrane along the length direction by using tweezers.
4. The method of preparing a dyed viscose cellulose proton exchange membrane for a fuel cell according to claim 1 or 2, wherein: and (2) soaking the viscose fiber membrane obtained in the step (1) in a 2-3 wt% NaOH solution for 30-40 min, preparing a 40-45 g/L2, 3-epoxypropyltrimethylammonium chloride solution, soaking the soaked viscose fiber membrane in the 2, 3-epoxypropyltrimethylammonium chloride solution for 30-40 min, then carrying out double-soaking and double-rolling, baking the viscose fiber membrane in an oven at 110-120 ℃ for 3-4 min, and naturally cooling.
5. The method of preparing a dyed viscose cellulose proton exchange membrane for a fuel cell according to claim 1 or 2, wherein: weighing 1-4 owf% of X-2R type reactive dye to prepare dye liquor, wherein the weight ratio of the dye liquor to the bath is 1: 40-50 putting the viscose fiber membrane obtained in the step (2) into the dye liquor, dyeing for 30-40 min at room temperature, putting the beaker into a constant-temperature water bath, slowly heating to 50-60 ℃, adding sodium carbonate for color fixing treatment, wherein the concentration of the sodium carbonate is 10-15 g/L, taking out the beaker after 30-40 min, naturally cooling at room temperature, washing the viscose fiber membrane with deionized water, soaping, washing with deionized water, washing off loose colors, and naturally airing and storing for later use.
6. The method of preparing a dyed viscose cellulose proton exchange membrane for a fuel cell according to claim 1 or 2, wherein: in the step (3), 3 owf% of X-2R type reactive dye is weighed to prepare dye liquor.
7. The method of preparing a dyed viscose cellulose proton exchange membrane for a fuel cell according to claim 1 or 2, wherein: in the step (3), the molecular structural formula of the 3 owf% X-2R type reactive dye is shown as the following formula,
8. the method of preparing a dyed viscose cellulose proton exchange membrane for a fuel cell according to claim 1 or 2, wherein: the thickness of the dyed cellulose proton exchange membrane for the fuel cell is 100-150 mu m.
9. The method of preparing a dyed viscose cellulose proton exchange membrane for a fuel cell according to claim 1 or 2, wherein: the coagulation bath has a composition of 118g/L H2SO4、320g/L Na2SO4And 11g/L ZnSO4。
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| US20070077478A1 (en) * | 2005-10-03 | 2007-04-05 | The Board Of Management Of Saigon Hi-Tech Park | Electrolyte membrane for fuel cell utilizing nano composite |
| US20160251489A1 (en) * | 2013-11-01 | 2016-09-01 | Institute Of Chemistry, Chinese Academic Of Sciences | Regenerated cellulose film, functional film and preparation method therefor |
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| CN109400942A (en) * | 2018-11-23 | 2019-03-01 | 瑞智新材(深圳)有限公司 | A kind of composite microporous film and preparation method thereof |
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| CN1682390A (en) * | 2002-09-18 | 2005-10-12 | 锌矩阵动力公司 | Method for manufacture of films containing insoluble solids embedded in cellulose-based films |
| US20070077478A1 (en) * | 2005-10-03 | 2007-04-05 | The Board Of Management Of Saigon Hi-Tech Park | Electrolyte membrane for fuel cell utilizing nano composite |
| US20160251489A1 (en) * | 2013-11-01 | 2016-09-01 | Institute Of Chemistry, Chinese Academic Of Sciences | Regenerated cellulose film, functional film and preparation method therefor |
| CN105968398A (en) * | 2016-05-12 | 2016-09-28 | 盐城工学院 | {0><}0{>Low-temperature alkaline fuel cell anion exchange membrane and preparation method thereof |
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