CN114960207A - Perfluorosulfonic acid carbon fiber composite material and preparation method and application thereof - Google Patents
Perfluorosulfonic acid carbon fiber composite material and preparation method and application thereof Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a perfluorosulfonic acid carbon fiber composite material, and a preparation method and application thereof. The perfluorosulfonic acid carbon fiber composite material is prepared by treating carbon fiber prepreg with salt type perfluorosulfonic acid resin dispersion liquid. The preparation method of the composite material comprises the following steps: (1) preparing carbon fiber prepreg; (2) preparing an alcohol-water dispersion of salt type perfluorosulfonic acid resin; (3) treating the carbon fiber prepreg in the step (1) by spraying or dipping the dispersion liquid in the step (2). By treating the carbon fibers with the alcohol-water dispersion of the salt-type perfluorosulfonic acid resin, not only can the initial strength of the carbon fibers be maintained, but also the surface is smooth, and during long-term hydrogen storage, the surface of the carbon fibers is smooth and the strength attenuation rate thereof is reduced from 70% to 10% based on the excellent hydrogen blocking effect of the salt-type perfluorosulfonic acid resin layer.
Description
Technical Field
The invention relates to a high-performance carbon fiber composite material, in particular to a perfluorosulfonic acid carbon fiber composite material, a preparation method and application thereof.
Background
The hydrogen energy is an energy form with great prospect in the future, and the hydrogen storage is an intermediate link of the hydrogen energy industry and is very critical, so the hydrogen energy storage and transportation technology has very important significance for the research of the hydrogen storage and transportation technology. Hydrogen storage in high pressure hydrogen cylinders is currently the most predominant way of storing hydrogen in gaseous form. The internal pressure of the early traditional hydrogen storage bottle is only 13.5MPa, the hydrogen storage density is less than 3 percent, and the early traditional hydrogen storage bottle cannot be applied to the civil field. The bottle is developed to civil use at the present stage, and goes through four generations, and the first-generation bottle is an all-metal bottle, and the pressure resistance is not more than 30 MPa. The second generation bottle and the third generation bottle are made of composite materials for external use of a metal inner container, the second generation bottle is made of a steel inner container and carbon fiber wound, the third generation bottle is made of an aluminum inner container and carbon fiber wound, and the pressure resistance can be improved to 70 MPa. The inner container of the latest hydrogen storage bottle, namely the fourth generation bottle, is made of high polymer materials, the whole bottle body is wrapped by fiber reinforced resin composite materials, and the bottle mouth is made of metal. The innermost layer of the fourth generation bottle is directly contacted with hydrogen to form a gas barrier layer, the thickness of the gas barrier layer is about 2-3mm, and the gas barrier layer is an olefin (EVOH) plastic polymer and plays a role in blocking hydrogen. The middle layer of the fourth generation bottle is a relatively thick pressure-resistant layer made of carbon fiber reinforced composite material and composed of carbon fiber and epoxy resin. As the hydrogen in the gas storage cylinder is consumed, the main body also shrinks along with the reduction of pressure, the fatigue of the material can be caused by the high-pressure environment and repeated inflation and deflation, and the permeated hydrogen affects the material, so that the material becomes brittle, the strength is reduced, the pressure-resistant grade is reduced, and the service life of the hydrogen storage cylinder is shortened. On the premise of ensuring the pressure-resistant grade, the thickness of the layer is reduced as much as possible to improve the hydrogen storage efficiency. The outermost layer is a surface protection layer with the thickness of about 2-3mm, and the material is a glass fiber reinforced composite material and is composed of glass fiber and epoxy resin.
The carbon fiber is an inorganic fiber formed by cracking and carbonizing an organic fiber at a high temperature to form a carbon main chain mechanism, and is an inorganic fiber with carbon content higher than 90%. Carbon fibers used in the field of hydrogen storage are mainly Polyacrylonitrile (PAN) -based carbon fibers. Since the price of the carbon fiber for the hydrogen storage bottle significantly affects the manufacturing cost of the hydrogen storage bottle, how to improve the service life of the carbon fiber is one of the hot points of continuous attention in the hydrogen storage field.
In the field of hydrogen production, the perfluorosulfonic acid resin membrane is widely applied as a proton exchange membrane in the fields of fuel cells, hydrogen production by water electrolysis and the like due to excellent thermal stability, chemical stability, high mechanical strength and high industrialization degree. A perfluorosulfonic acid resin film having a hydrogen gas permeability of 10 -11 -10 -10 The gas permeability is quite low in the order of mol/(cm.s.atm), and the oxygen gas permeability of EVOH currently used is 10 -6 The mol/(cm.s.atm) order, the barrier property of the perfluor sulfonic acid resin film to hydrogen is greatly superior to that of the polyolefin material. For perfluorosulfonic acid resin, Nafion series solution of DuPont company in the United states is mainly sold on the market at present, the adopted solvent is a water-isopropanol system, the solution is not suitable for being directly used for preparing a proton exchange membrane, and the prepared membrane is easy to become brittle and has unsatisfactory mechanical strength.
The carbon fiber epoxy resin composite material composed of carbon fiber and epoxy resin used in the existing hydrogen storage bottle has the defects of brittle material, reduced strength, reduced pressure rating and reduced service life in the hydrogen storage process, so the development of the carbon fiber composite material with higher strength and longer service life for the hydrogen storage field is urgently needed.
Disclosure of Invention
The invention aims to provide a perfluorosulfonic acid carbon fiber composite material, and a preparation method and application thereof. The perfluorosulfonic acid carbon fiber composite material has good barrier effect on hydrogen and can be used for manufacturing IV-generation hydrogen storage bottles.
In one aspect, the invention provides a perfluorosulfonic acid carbon fiber composite material, which is prepared by treating a carbon fiber prepreg with a salt-type perfluorosulfonic acid resin dispersion liquid.
Among them, carbon fibers of T300 grade or more are selected as the carbon fibers, and carbon fibers of T700 grade or more are preferable. Specific examples of the carbon fiber are T300-grade, T700-grade, T800-grade, T1000-grade, and T1100-grade carbon fibers.
The salt type perfluorosulfonic acid resin is obtained by reacting a perfluorosulfonic acid resin containing a xanthyl functional group with a base (hydroxide) to introduce metal ions into the perfluorosulfonic acid resin. The metal ion is selected from Li, Na, K, Rb, Cs, Mn, Zn, Ti, Cr, Fe, Co, Ni, Cu, Zr, Pd, Pt, W, etc., preferably Na, K. The EM of the salt type perfluorosulfonic acid resin used in the invention is 800-1500g/mol, such as 800g/mol,830g/mol,850g/mol,880g/mol,900g/mol,930g/mol,950g/mol,980g/mol,1000g/mol,1050g/mol,1100g/mol,1200g/mol,1300g/mol,1400g/mol and 1500 g/mol. The perfluorosulfonic acid resins useful in the present invention are well known to those skilled in the art and are obtained by copolymerizing perfluorosulfonyl enol ether monomer with tetrafluoroethylene. The perfluorosulfonic acid resin is commercially available, for example from DuPont
Of the dow type
Of Asahi
And
and so on.
The types and preparation methods of salt-type perfluorosulfonic acid resins can be found in, for example, CN101759858A, CN101794888A, both of which are incorporated herein in their entirety.
On the other hand, the invention provides a preparation method of the perfluorosulfonic acid carbon fiber composite material, which comprises the following steps:
(1) preparing carbon fiber prepreg;
(2) preparing an alcohol-water dispersion of salt type perfluorosulfonic acid resin;
(3) treating the carbon fiber prepreg in the step (1) by spraying or dipping the dispersion liquid in the step (2).
Preferably, the step (1) includes: and (3) impregnating or spraying a sizing agent on the carbon fiber tows, drying at the temperature of 170-190 ℃ for 40-100s, and rolling to obtain the carbon fiber prepreg.
Preferably, step (1) comprises: impregnating carbon fiber tows by using bisphenol A epoxy resin as a main sizing agent, drying at 180 ℃ for 60s, and rolling.
Among them, carbon fibers of T300 or more are preferable, and carbon fibers of T700 or more are more preferable. More preferably, the carbon fibers are of T300 grade, T700 grade, T800 grade, T1000 grade, and T1100 grade.
Preferably, the step (2) includes: drying the salt type perfluorinated sulfonic acid resin in vacuum, adding the salt type perfluorinated sulfonic acid resin into an autoclave, adding pure water and C1-C4 alcohol, setting the dissolving temperature at 200-280 ℃, stirring at the speed of 100-1000 r/min, and dissolving in the autoclave to obtain the prepared dispersion liquid.
Preferably, the salt type perfluorosulfonic acid resin is dried in vacuum at 60-100 ℃ for 1-6h, 4-12 parts of the salt type perfluorosulfonic acid resin is added into an autoclave, 30-70 parts of pure water and 70-30 parts of C1-C4 alcohol are added, the dissolving temperature is set to 250-.
Preferably, the salt type perfluorosulfonic acid resin is dried in vacuum at 80 ℃ for 4h, 5-10 parts of the salt type perfluorosulfonic acid resin is added into an autoclave, 30-70 parts of pure water and 70-30 parts of C1-C4 alcohol are added, the dissolving temperature is set at 250 ℃ and the stirring speed is set at 200-800 r/min, and the solution is dissolved in the autoclave for 2-4h to obtain the prepared dispersion liquid.
Wherein, the C1-C4 alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol or tert-butanol. The pure water is the pure water which accords with the water specification GB6682-92 for the national laboratory in China. The autoclave is made of Hastelloy.
Preferably, step (3) comprises: and (3) coating the alcohol-water dispersion liquid of the salt type perfluorosulfonic acid resin in the step (2) on the carbon fiber prepreg by adopting an impregnation or spraying process, and curing and molding at the temperature of 60-80 ℃.
On the other hand, the invention protects the perfluorosulfonic acid carbon fiber composite material and the application of the perfluorosulfonic acid carbon fiber composite material prepared by the method in the preparation of hydrogen storage bottles.
The applicant has found through research that two types of dispersions which are most commonly used at present are perfluorosulfonic acid DMF dispersion and Nafion solution (hydro-alcoholic system hydrogen type), and both an organic solvent and a strong acid in the dispersions can damage carbon fibers to different degrees, so that the process cannot be applied to the dispersions. And the salt type perfluorinated sulfonic acid resin can avoid the damage of organic solvent and strong acid to the carbon fiber. The perfluorinated sulfonic acid resin has good compatibility of a sulfonate group and the treated carbon fiber, and is not easy to strip.
The invention has the beneficial technical effects that: by treating the carbon fibers with the alcohol-water dispersion of the salt-type perfluorosulfonic acid resin, not only can the initial strength of the carbon fibers be maintained, but also the surfaces of the carbon fibers are smooth, and in the long-term hydrogen storage process, the surfaces of the carbon fibers are smooth, the tensile strength attenuation rate is reduced to 10% based on the excellent hydrogen blocking effect of the salt-type perfluorosulfonic acid resin layer, and the composite material has excellent hydrogen storage performance.
Drawings
Fig. 1 is a surface topography of the water-alcohol salt type perfluorosulfonic acid carbon fiber composite material of example 1 under a microscope (160 times).
Fig. 2 is a surface topography of the water-alcohol salt type perfluorosulfonic acid carbon fiber composite material of example 2 under a microscope (160 times).
Fig. 3 is a surface topography under a microscope (160 x) of a raw carbon fiber prepreg of comparative example 1.
FIG. 4 is a surface topography under a microscope (160 times) of the DMF type perfluorosulfonic acid carbon fiber composite material of comparative example 2.
FIG. 5 is a surface topography under a microscope (160 times) of the hydroalcoholic hydrogen-type perfluorosulfonic acid carbon fiber composite material of comparative example 3.
FIG. 6 is a surface topography under a microscope (160 times) of the hydroalcoholic hydrogen-type perfluorosulfonic acid carbon fiber composite material of comparative example 4.
Detailed Description
The invention is further illustrated with reference to the following examples, without however limiting the scope of the invention as claimed.
Example 1: synthesis of water-alcohol salt type perfluor sulfoacid carbon fiber composite material (coating process by spraying)
(1) And (3) synthesizing a carbon fiber prepreg: supernatural hawk T700 carbon fiber (3K) tows are impregnated by taking bisphenol A epoxy resin as a main sizing agent, dried for 60s at 180 ℃, and rolled to obtain the carbon fiber prepreg.
(2) Sodium perfluorosulfonic acid resin (EW 1050g/mol) is dried in vacuum at 80 ℃ for 4h, 5g of resin is added into a Hastelloy material autoclave, 45g of pure water, 50g of isopropanol and 5g of ethanol are added, the dissolving temperature is set at 250 ℃, the stirring speed is 500 r/min, and the resin is dissolved in the autoclave for 3h, so that 5% sodium-hydroalcoholic perfluorosulfonic acid resin dispersion liquid is obtained.
(3) And (3) coating the carbon fiber impregnated material in the step (1) with the dispersion liquid in the step (2) in a spraying mode, and curing at 60 ℃ to obtain the water-alcohol salt type (sodium type) carbon fiber perfluorinated sulfonic acid resin composite material.
According to the test, in example 1, a spraying mode is adopted, 2.5g of water-alcohol-sodium type perfluorosulfonic acid resin dispersion liquid is sprayed on 10 carbon fiber prepregs with the length of 30cm, the dried mass is 1.04g, the sizing amount is 8.4%, the initial tensile strength of the obtained water-alcohol-sodium type carbon fiber perfluorosulfonic acid resin composite material is 158MPa, and the tensile strength is 143MPa after the composite material is stored for 45 days in a normal pressure hydrogen environment.
FIG. 1 is a surface topography of the composite material obtained using a microscope (160X).
Example 2: synthesis of water-alcohol salt type perfluor sulfoacid carbon fiber composite material (coating process by impregnation)
(1) And (3) synthesizing a carbon fiber prepreg: supernatural hawk T700 carbon fiber (3K) tows are impregnated by using bisphenol A epoxy resin as a main sizing agent, dried for 60s at 180 ℃, and rolled to obtain the carbon fiber prepreg.
(2) Sodium perfluorosulfonic acid resin (EW 1050g/mol) is dried in vacuum at 80 ℃ for 4h, 8g of resin is added into a Hastelloy material autoclave, 45g of pure water, 50g of isopropanol and 5 parts of ethanol are added, the dissolving temperature is set at 260 ℃, the stirring speed is 800 r/min, and the resin is dissolved in the autoclave for 4h, so that 8% sodium-alcohol-type perfluorosulfonic acid resin dispersion liquid is obtained.
(3) And (3) coating the carbon fiber prepreg obtained in the step (1) with the dispersion liquid obtained in the step (2) in an impregnation mode, and curing at 80 ℃ to obtain the water-alcohol salt type (sodium type) carbon fiber perfluorosulfonic acid resin composite material.
Through testing, in example 2, an impregnation mode is adopted, 10 carbon fiber prepregs with the length of 30cm are impregnated into 10mL of water-alcohol-sodium type perfluorinated sulfonic acid resin dispersion liquid, the dried carbon fiber prepregs with the length of 30cm have the mass of 1.82g, the sizing amount is 90%, the initial tensile strength of the obtained water-alcohol-sodium type carbon fiber perfluorinated sulfonic acid resin composite material is 178MPa, and the tensile strength of the obtained water-alcohol-sodium type carbon fiber perfluorinated sulfonic acid resin composite material after being stored for 45 days in a normal pressure hydrogen environment is 165 MPa.
Fig. 2 is a surface topography of the composite material obtained using a microscope (160 x).
Comparative example 1:
using the carbon fiber prepreg used in example 1, the surface topography thereof obtained using a microscope (160 x) is given in fig. 3. The initial tensile strength of the carbon fiber prepreg was 174MPa, and the tensile strength after storage for 45 days under a normal pressure hydrogen atmosphere was 53 MPa.
Comparative example 2: synthesis of DMF type perfluorosulfonic acid carbon fiber composite material (coating process by dipping)
(1) And (3) synthesizing a carbon fiber prepreg: supernatural hawk T700 carbon fiber (3K) tows are impregnated by using bisphenol A epoxy resin as a main sizing agent, dried for 60s at 180 ℃, and rolled to obtain the carbon fiber prepreg.
(2) Hydrogen type perfluorosulfonic acid resin (EW 1050g/mol) is dried in vacuum at 80 ℃ for 4h, 5g of resin is added into a Hastelloy material autoclave, 100g of DMF is added, the dissolving temperature is set at 80 ℃, the stirring speed is 200 r/min, and the resin is dissolved in the autoclave for 4h, so that 5% DMF type perfluorosulfonic acid resin dispersion liquid is obtained.
(3) And (3) coating the carbon fiber prepreg obtained in the step (1) with the dispersion liquid obtained in the step (2) in an impregnation mode, and curing at 60 ℃ to obtain the DMF type perfluorosulfonic acid carbon fiber composite material.
According to the test, the method of dipping is adopted in the comparative example 2, 10 carbon fiber prepregs with 30cm are dipped in 10mL of perfluorosulfonic acid dispersion liquid, the dried mass is 1.34g, the sizing amount is 42%, the initial tensile strength of the obtained DMF type perfluorosulfonic acid carbon fiber composite material is 93MPa, and the tensile strength is 76MPa after the DMF type perfluorosulfonic acid carbon fiber composite material is stored for 45 days under the normal pressure hydrogen environment.
Fig. 4 is a surface topography of the composite material obtained using a microscope (160 x).
Comparative example 3: synthesis of hydroalcoholic hydrogen perfluorosulfonic acid carbon fiber composite material (coating process by spraying)
(1) Synthesis of carbon fiber prepreg: supernatural hawk T700 carbon fiber (3K) tows are impregnated by using bisphenol A epoxy resin as a main sizing agent, dried for 60s at 180 ℃, and rolled to obtain the carbon fiber prepreg.
(2) Hydrogen type perfluorosulfonic acid resin (EW 1050g/mol) is dried in vacuum at 80 ℃ for 4h, 5g of the resin is added into a hastelloy material autoclave, 45g of pure water, 50g of isopropyl alcohol and 5g of ethanol are added, the dissolving temperature is set at 250 ℃, the stirring speed is 500 r/min, and the resin is dissolved in the autoclave for 2h, so that 5% water-alcohol-hydrogen type perfluorosulfonic acid resin dispersion liquid is obtained.
(3) And (3) coating the dispersion liquid obtained in the step (2) with the carbon fiber prepreg obtained in the step (1) in a spraying mode, and curing at 60 ℃ to obtain the hydro-alcoholic hydrogen type perfluorosulfonic acid carbon fiber composite material.
According to the test, the comparative example 3 adopts a spraying mode, 2.5g of water-alcohol-hydrogen type perfluorosulfonic acid resin dispersion liquid is sprayed on 10 carbon fiber prepregs with the length of 30cm, the dried mass is 1.05g, the sizing amount is 8.9%, the initial tensile strength of the obtained water-alcohol-hydrogen type perfluorosulfonic acid carbon fiber composite material is 115MPa, and the tensile strength is 111MPa after the composite material is stored for 45 days in a normal-pressure hydrogen environment.
Fig. 5 is a surface topography of the composite material obtained using a microscope (160 x).
Comparative example 4: synthesis of hydroalcoholic hydrogen type perfluorosulfonic acid carbon fiber composite material (coating process by dipping)
(1) And (3) synthesizing a carbon fiber prepreg: supernatural hawk T700 carbon fiber (3K) tows are impregnated by using bisphenol A epoxy resin as a main sizing agent, dried for 60s at 180 ℃, and rolled to obtain the carbon fiber prepreg.
(2) The hydrogen type perfluorosulfonic acid resin (EW is 1050g/mol) is dried in vacuum at 80 ℃ for 4h, 8g of the resin is added into a Hastelloy material autoclave, 45g of pure water, 50g of isopropanol and 5g of ethanol are added, the dissolution temperature is set at 270 ℃, the stirring speed is 800 r/min, and the resin is dissolved in the autoclave for 3h, so that 8% hydro-alcoholic perfluorosulfonic acid resin dispersion liquid is obtained.
(3) And (3) coating the carbon fiber prepreg obtained in the step (1) with the dispersion liquid obtained in the step (2) in an impregnation mode, and curing at 80 ℃ to obtain the hydro-alcoholic hydrogen type perfluorosulfonic acid carbon fiber composite material.
According to the test, the method of impregnation is adopted in the comparative example 4, 10 carbon fiber prepregs with 30cm are immersed in 10mL of water-alcohol-hydrogen type perfluorosulfonic acid resin dispersion liquid, the dried carbon fiber prepregs with 30cm carbon fiber prepregs have the mass of 1.89g, the sizing amount is 97%, the initial tensile strength of the obtained water-alcohol-hydrogen type perfluorosulfonic acid carbon fiber composite material is 149MPa, and the tensile strength of the obtained water-alcohol-hydrogen type perfluorosulfonic acid carbon fiber composite material after the composite material is stored for 45 days in a normal pressure hydrogen environment is 91 MPa.
Fig. 6 is a surface topography of the composite material obtained using a microscope (160 x).
For comparison, table 1 summarizes the relevant process and experimental results for examples 1-2 and comparative examples 1-4.
TABLE 1
The experimental result shows that when the raw carbon fiber prepreg is not treated, the initial tensile strength is 174MPa, the tensile strength is reduced to 53MPa after the raw carbon fiber prepreg is stored in a hydrogen environment for 45 days, the reduction amplitude reaches 121MPa, and the performance attenuation reaches 70 percent, which indicates that the tensile strength is greatly reduced by adopting the untreated carbon fiber prepreg, and the service life of the carbon fiber prepreg is influenced.
As can be seen from fig. 1 to 6, the DMF type perfluorosulfonic acid resin dispersion of comparative example 2 damaged the carbon fiber prepreg and had cracks on the surface. The aqueous-alcoholic-hydrogen-type perfluorosulfonic acid resin dispersions of comparative examples 3 to 4 caused some damage to the carbon fibers, and surface burrs. The water-alcohol salt type perfluorinated sulfonic acid resin dispersion liquid does not damage the carbon fiber and has smooth surface.
In addition, the sizing amount by the dipping process is obviously higher than that by the spraying process, and the sizing amount of the hydroalcoholic type is obviously higher than that of the DMF type perfluorosulfonic acid resin dispersion liquid of comparative example 2. Even if the coating process of impregnation is used, the sizing amount of the DMF type perfluorosulfonic acid resin dispersion is only 42%. Correspondingly, the sizing amounts of the water-alcohol-hydrogen type perfluorosulfonic acid resin dispersion liquid and the water-alcohol-salt type perfluorosulfonic acid resin dispersion liquid respectively reach 97% and 90% by adopting the coating process of impregnation.
The DMF type perfluorosulfonic acid resin dispersion damaged the carbon fiber prepreg, and the initial strength of the obtained composite material was 93MPa, which was reduced by nearly 50% relative to 174MPa for the original carbon fiber. After being stored in a hydrogen environment for 45 days, the tensile strength is reduced from 93MPa to 76MPa, and the reduction amplitude is 17 MPa.
The hydroalcoholic hydrogen type perfluorosulfonic acid resin dispersion liquid causes damage to the carbon fiber prepreg to a certain extent, has burrs on the surface, and the initial strength of the obtained composite material is 115MPa (spraying process) and 149MPa (dipping process), and is also greatly reduced compared with 174MPa of the original carbon fiber. After the carbon fiber is stored in a hydrogen environment for 45 days, the tensile strength is 111MPa and 91MPa respectively, the change range of the tensile strength of the spraying process is not large, but the dipping process is obviously reduced, and the carbon fiber is greatly damaged by dipping.
The water-alcohol salt type perfluorinated sulfonic acid resin dispersion liquid does not damage carbon fibers, the surface is smooth, the initial strength of the obtained composite material is 158MPa (spraying process) and 178MPa (dipping process), and the initial strength change is not obvious compared with 174MPa of the original carbon fibers. After being stored in a hydrogen environment for 45 days, the tensile strength is 143MPa and 165MPa respectively, the tensile strength is slightly reduced, the attenuation rate is reduced from 70 percent to 10 percent, and the performance is greatly improved.
In summary, the DMF type perfluorosulfonic acid resin dispersion liquid damages the carbon fiber prepreg, has obvious cracks on the surface, has low sizing amount, reduces the initial strength by about 50%, and is not suitable for processing the carbon fiber. The hydro-alcoholic hydrogen type perfluorosulfonic acid resin dispersion liquid causes damage to carbon fibers to a certain extent, surface burrs and initial strength are greatly reduced, so that the hydro-alcoholic hydrogen type perfluorosulfonic acid resin dispersion liquid is not suitable for treating carbon fiber prepregs. The water-alcohol salt type perfluorinated sulfonic acid resin dispersion liquid does not damage the carbon fiber prepreg, the surface is smooth, and the initial strength change is not obvious. After being placed in a hydrogen environment for 45 days, the tensile strength decay rate is reduced to 10 percent from 70 percent without treatment, and the excellent hydrogen storage performance is shown.
While one or more embodiments have been described with reference to the accompanying drawings, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope defined by the following claims and their equivalents.
Claims (17)
1. A perfluorosulfonic acid carbon fiber composite material is prepared by treating a carbon fiber prepreg with a salt perfluorosulfonic acid resin dispersion liquid.
2. The composite material according to claim 1, wherein the salt-forming metal in the salt-type perfluorosulfonic acid resin is selected from Li, Na, K, Rb, Cs, Mn, Zn, Ti, Cr, Fe, Co, Ni, Cu, Zr, Pd, Pt, or W.
3. The composite material according to claim 1 or 2, wherein the EW of the salt-type perfluorosulfonic acid resin is 800-1500 g/mol.
4. The composite material of claim 1 or 2, wherein the EW of the salt-type perfluorosulfonic acid resin is selected from 800g/mol,830g/mol,850g/mol,880g/mol,900g/mol,930g/mol,950g/mol,980g/mol,1000g/mol,1050g/mol,1100g/mol,1200g/mol,1300g/mol,1400g/mol, or 1500 g/mol.
5. The composite material according to claim 1 or 2, wherein the carbon fiber is a carbon fiber of T300 grade or more.
6. The composite material according to claim 5, wherein the carbon fiber is a carbon fiber of T700 grade or more.
7. The composite material according to claim 5, wherein the carbon fibers are selected from carbon fibers of T300 grade, T700 grade, T800, T1000 grade or T1100 grade.
8. A method of preparing a composite material according to any one of claims 1 to 7, comprising the steps of:
(1) preparing carbon fiber prepreg;
(2) preparing an alcohol-water dispersion of salt type perfluorosulfonic acid resin;
(3) treating the carbon fiber prepreg in the step (1) by spraying or dipping the dispersion liquid in the step (2).
9. The method of claim 8, wherein the step (1) comprises: and (3) dipping or spraying a sizing agent on the carbon fiber tows, drying at the temperature of 170-190 ℃ for 40-100s, and rolling to obtain the carbon fiber prepreg.
10. The method of claim 9, wherein the step (1) comprises: and (3) impregnating the carbon fiber tows by adopting bisphenol A epoxy resin as a main sizing agent, and drying at 180 ℃ for 60 s.
11. The method of claim 8, wherein the step (2) comprises: drying the salt type perfluorinated sulfonic acid resin in vacuum, adding the salt type perfluorinated sulfonic acid resin into an autoclave, adding pure water and C1-C4 alcohol, setting the dissolving temperature at 200-280 ℃, stirring at the speed of 100-1000 r/min, and dissolving in the autoclave to obtain the prepared dispersion liquid.
12. The method of claim 11, wherein the step (2) comprises: vacuum drying salt type perfluorosulfonic acid resin at 60-100 ℃ for 1-6h, adding 4-12 parts of salt type perfluorosulfonic acid resin into an autoclave, adding 30-70 parts of pure water and 70-30 parts of C1-C4 alcohol, setting the dissolving temperature at 250 ℃ and 260 ℃, stirring at 200-800 r/min, and dissolving in the autoclave for 2-4h to obtain the prepared dispersion liquid.
13. The method of claim 12, wherein the step (2) comprises: vacuum drying the salt type perfluorinated sulfonic acid resin at 80 ℃ for 4h, adding 5-10 parts of the salt type perfluorinated sulfonic acid resin into an autoclave, adding 30-70 parts of pure water and 70-30 parts of C1-C4 alcohol, setting the dissolving temperature at 250 ℃ and the stirring speed at 200-800 r/min, and dissolving in the reaction kettle for 2-4h to obtain the prepared dispersion liquid.
14. The process of any one of claims 11-13, wherein the C1-C4 alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, or tert-butanol.
15. The method according to any one of claims 8-13, wherein the autoclave is of hastelloy material.
16. The method of any one of claims 8-13, wherein step (3) comprises: and (3) coating the alcohol-water dispersion liquid of the salt type perfluorosulfonic acid resin in the step (2) on the carbon fiber prepreg by adopting an impregnation or spraying process, and curing and molding at the temperature of 60-80 ℃.
17. Use of the perfluorosulfonic acid carbon fiber composite material according to any one of claims 1 to 7 and the perfluorosulfonic acid carbon fiber composite material produced by the production method according to any one of claims 8 to 16 for the production of hydrogen storage bottles.
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