CN114249911A - Fiber-reinforced polyimide-based composite material and preparation method thereof - Google Patents
Fiber-reinforced polyimide-based composite material and preparation method thereof Download PDFInfo
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- CN114249911A CN114249911A CN202111500318.2A CN202111500318A CN114249911A CN 114249911 A CN114249911 A CN 114249911A CN 202111500318 A CN202111500318 A CN 202111500318A CN 114249911 A CN114249911 A CN 114249911A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 53
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 67
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 54
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- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 4
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 description 1
- YFBMJEBQWQBRQJ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=CC=C1 YFBMJEBQWQBRQJ-UHFFFAOYSA-N 0.000 description 1
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 description 1
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- XAEMLZHQTMMULC-UHFFFAOYSA-N n,n'-dimethyl-1,1-diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(NC)(NC)C1=CC=CC=C1 XAEMLZHQTMMULC-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a fiber reinforced polyimide-based composite material and a preparation method thereof. The method comprises the following specific steps: preparing a polyamic acid solution with certain viscosity by adopting an in-situ polymerization method; then continuously stirring the carbon chopped fibers into a homogeneous phase to prepare a carbon chopped fiber/PAA composite solution, suspending the composite solution on a flat carrier, then placing the flat carrier in a gel mixed solution for gelation, or orderly suspending carbon fiber cloth in the solution for taking out, then uniformly spraying the rest solution on two surfaces of the fibers, and compacting the two surfaces; then putting the composite piece in an oven for imidization treatment to obtain a polyimide-based reinforced composite material; and finally, placing the workpiece in a tubular furnace for high-temperature carbonization treatment to obtain the N-doped fiber reinforced polyimide-based carbonized composite material. The method has the advantages of controllable process, excellent process and basically consistent performance of two surfaces of the product, and the prepared composite material has good thermal conductivity and electrochemical characteristics and can be applied to the energy storage fields of supercapacitors, flexible electrodes and the like.
Description
Technical Field
The invention relates to a fiber reinforced polyimide-based composite material and a preparation method thereof, in particular to a polyimide matrix material modified by high-temperature carbonization and fiber reinforcement and a preparation method thereof.
Background
With the accelerated development of electronic information energy sources, the development of some basic electronic components in the field is also very rapid. In compliance with the requirements of new technologies, the conventional electronic components have been unable to meet the requirements of large environments. Under the influence of large economic environment, the capacitor energy storage industry has faced a great increase in cost in various aspects such as manpower, materials, environmental energy and the like, but the price of the product is gliding all the way, and under the combined action of the double pressure, electronic components need to be innovated comprehensively, so that the development requirements of the electronic industry can be met. The new electronic components represent the development trend of high-frequency, chip, miniaturization, thinning, low power consumption, high response speed, compounding, intellectualization and the like of the electronic components at present and in future.
The super capacitor is a novel energy storage device with the advantages of high energy density, rapid charge and discharge, long cycle life, high reliability, environmental protection and the like, and is paid attention by researchers in recent years. With the development of new energy and the requirements of digitalization and informatization environment, an energy storage device not only needs to have better cycle life, high specific energy and high specific power, but also needs to have light weight, portability and environmental stability, which are new challenges faced by the traditional capacitor. The electrode is used as the core part of the energy storage device, and the quality of the performance of the electrode plays a crucial role in the whole energy storage system. The carbon fiber not only becomes an advantageous material of the traditional carbon-based electrode of the energy storage equipment by virtue of excellent structural characteristics, but also is an irreplaceable core material in the fields of aerospace and national defense. Polyimide, one of the best engineering plastics in the world at present, is always on the top of a material pyramid regardless of a resin matrix or a composite material, and becomes a favorite in the emerging field. Therefore, the method is close to the application trend, develops a high-performance electrode suitable for a flexible energy storage device, and links the two materials strongly and strongly, so that the quality of the traditional capacitor component is reduced, the environmental stability of the electrode material is improved, the wide application of the composite material in energy storage equipment in the advanced field can be developed, and meanwhile, more technologies and material supports are provided for accelerating and improving the matching devices of the energy storage equipment, promoting the vigorous development of new energy equipment.
Yu Sheng Wang et al provides a simple, effective and practical method for preparing a porous flexible electrode. The electrode has excellent volume capacitance and surface capacitance. Graphene Oxide (RGO) with a proper size is mainly doped into nylon 66(PA66) nanofiber fabric with a high specific surface area, the synthesized RGO/PA66 nanofiber fabric has satisfactory electric conductivity and flexibility and adhesion between the RGO and PA66 nanofiber fabric, the RGO has a strong effect between conduction bands due to the large surface area of the nanofiber fabric, no agglomeration exists, and the specific mass capacitance (C) of the nanofiber fabric is improvedS,M) Specific volume capacitance (C)S,V) And specific area capacitance (C)S,A) So that the superfine fiber fabric is used as a substrate instead of superfine fiber fabric. The results also show that the size of RGO is a key factor in promoting nanofiber webs. In a three-electrode system, medium-sized reduced graphene oxide M-RGO/PA66(279.82 Fg)-1) And small size S-RGO/PA66(65.4 Fg)-1) And large size L-RGO/PA66(95.3 Fg)-1) Compared with the prior art, the super capacitor assembled by the M-RGO/PA66 has extremely high battery C based on the combination of the advantages of RGO and the nano-fiber fabric substrateS,V，CS,AAnd a substrate CS,M38.79Fcm respectively-3，0.931Fcm-2And 71.98Fg-1These values exceed the values reported in the relevant literature. Thus, by utilizing nanofiber fabrics and RGO of appropriate size as flexible electrode materials, a conceptual approach is provided to enhance the mass content of graphene and the specific capacitance of the flexible electrode. However, the method has higher requirements on process conditions, higher indexes on temperature and pressure and strict requirements on preparation environment.
Zhang et al have guaranteed quick electron transfer through the porous carbon base aerogel frame that cellulose derived, and abundant micropore and active site are provided to outside PI layer, regard it as electrode material, through 10000 cycles charge-discharge, the electric capacity retention still reaches more than 90%. However, this method has a long period of time and has a certain limitation in the development of industrialization.
The Kunming technology university college of Material science and engineering adopts an electrodeposition method to prepare the carbon fiber laminated composite electrode material. Depositing compact and uniform beta-PbO on the surface of the carbon fiber electrode2And an active layer. The modified composite electrode has low oxygen evolution potential and excellent electrocatalytic activity. Compared with the traditional lead alloy electrode, the carbon fiber electrode has the advantages that the mass is reduced by 69.7%, the corrosion potential of the carbon fiber electrode is higher, the corrosion rate is lower, and the carbon fiber electrode has better corrosion resistance. However, the selection of the electrode for the electrolyte is relatively single, and the application of the material in the field of energy storage is limited to a certain extent.
Winthrop et al used a carbon fiber composite polyimide material in a neuro-engineering response electrode material. The magnitude of the response to nerves is related to the electrode size (especially cross-sectional area), the relative stiffness of the electrode, and the tissue tolerance of the material. The flexible carbon fiber ultramicroelectrode has a much smaller cross section and lower tissue reactivity than conventional electrodes. Researchers have facilitated the construction of high density recording and excitation transmission arrays by assembling carbon fiber electrodes on flexible polyimide substrates. Meanwhile, indium is deposited on the carbon fiber for low-temperature micro-melting, and a reliable electrical connection method is provided for polyimide interconnection. In addition, the generally poor charge injection capability of small diameter carbon fibers is improved by electrodepositing a 100nm thick iridium oxide film, allowing the carbon fiber array to be used for both electrical stimulation and recording. The method paves the way for further miniaturization of the carbon fiber ultramicro electrode array in the manufacturing technology. And lays a foundation for the application of the carbon fiber reinforced polyimide resin matrix in the field of flexible electrodes. However, since the main research in this work is the relationship between the electrode material and the neural response, and there is a certain difference from the electron transport and conversion mechanism in the charge and discharge processes, there is still a need for further research, development and breakthrough of the application of this system material in electrochemical devices.
CN108365229A discloses a preparation method of a large-specific-surface-area N-doped carbon cloth electrode. The surface of the carbon cloth is subjected to porosification and functionalization treatment by respectively using argon and nitrogen through a magnetron sputtering back-sputtering technology. The method has large adherence to equipment, and lacks quantitative regulation and control on the parameter setting of the surface structure morphology of the electrode carrier material.
CN110724840A discloses a preparation method of a polyaniline/N-doped graphitized carbon composite conductive membrane electrode. Taking pretreated waste biomass sugarcane hawthorn as a raw material, and preparing N-doped graphitized carbon through alkali activation, N doping, pre-carbonization and high-temperature carbonization; and compounding N-doped graphitized carbon and a conductive polymer (polyaniline) to prepare the polyaniline/N-doped graphitized carbon composite conductive membrane electrode, wherein the polyaniline/N-doped graphitized carbon composite conductive membrane electrode has high specific surface area and good conductivity and chemical stability, and is high in extraction rate and good in adsorption selectivity of uranium in brine when used for extracting uranium from brine through electro-adsorption, and can meet the requirements of modern industrial production. However, the process does not well reflect the structural advantages of the carbon material after the pre-cured material is carbonized at high temperature, and the structural-effect correlation caused by structural reorganization after high-temperature carbonization is neglected only from the consideration of the conductivity of the material.
Disclosure of Invention
The invention aims to expand the application of a fiber reinforced polyimide composite material in electrochemistry and simultaneously improve the flexibility and good thermal conductivity of a traditional super capacitor, thereby providing the fiber reinforced polyimide composite material, and the invention also aims to provide a preparation method of the material.
The technical scheme of the invention is that the method for preparing the fiber (fabric) reinforced polyimide-based composite material with high electrochemical performance comprises the following steps:
A. preparation of carbon chopped fiber reinforced polyimide composite material
a1) Pretreatment of raw materials:
firstly, placing the carbon chopped fibers in an oven at the temperature of 100-150 ℃ for keeping the temperature constant for 1-4h, and removing moisture, volatile and easily decomposed components in the chopped fibers; then putting the chopped fibers into a reactor filled with a polar solvent, adding a coupling agent, controlling the temperature to be between room temperature and 50 ℃, and ultrasonically stirring for 0.5 to 1 hour with the frequency of 20KHz to 100 KHz;
b1) Preparation of Polyamic acid (PAA) solution
Referring to the patent "preparation method of polyimide hybrid film with high modulus and low thermal expansion coefficient" (ZL200810236233.6), adding a certain amount of diamine monomer and polar solvent, ultrasonically stirring, adding 3-7 batches of dianhydride with equimolar amount to the diamine monomer after the diamine monomer is completely dissolved, and continuously stirring for reaction for a certain time to prepare Polyimide (PAA) solution with stable performance;
c1) Preparation of carbon chopped fiber/PAA composite solution
A is to1Mixing the solution with b1Mixing the PAA solution, and continuously stirring to form a homogeneous phase to prepare a carbon chopped fiber/PAA composite solution;
d1) Preparation of carbon chopped fiber reinforced polyimide composite material part
C is to1The composite solution prepared in the step (1) is hung on a flat carrier, then the flat carrier is placed in a gel mixed solution for gelation, and a composite flat membrane material piece with a porous appearance is obtained after 1-12 hours.
Putting the workpiece into a high-temperature oven for drying treatment, firstly carrying out air blast drying at normal temperature for 1-2h, then carrying out step heating, heating to 280-320 ℃, keeping the temperature for 50-70min, and carrying out dehydration cyclization to obtain a carbon chopped fiber reinforced polyimide-based composite part;
e1) Preparation of high temperature carbonized materials
Will d1The composite member is placed in a reaction furnace with programmed temperature rise, and under the protection of inert gas, the temperature rises to 400-900 ℃ for carbonization treatment, so as to obtain an N-doped carbon fiber reinforced polyimide-based composite member;
B. preparation of carbon fiber cloth reinforced polyimide-based composite material part
a2) Pretreatment of raw materials:
firstly, placing the carbon fiber cloth in an oven at the temperature of 100-150 ℃ for keeping the constant temperature for 1-4h, and removing moisture, volatile and easily decomposed components in the chopped fibers; then placing the chopped fibers into a reactor filled with a polar solvent, controlling the temperature to be between room temperature and 50 ℃, keeping the frequency to be between 20KHz and 100KHz, ultrasonically stirring for 0.5 to 1 hour, and standing at normal temperature for later use;
b2) Preparation of Polyamic acid (PAA) solution
According to the patent of 'a preparation method of polyimide hybrid film with high modulus and low thermal expansion coefficient' (ZL200810236233.6), adding a certain amount of diamine monomer and a polar solvent, ultrasonically stirring, after completely dissolving, adding dianhydride with the same molar quantity with the diamine monomer in 3-7 batches, and continuously stirring and reacting for a certain time to prepare Polyimide (PAA) solution with stable performance;
c2) Preparation of PAA coated carbon fiber cloth composite part
A is to2In the carbon fiber cloth is suspended in the b2Taking out the PAA solution for 10-30 min. Then the rest b is2Uniformly spraying the solution on two sides of the carbon fiber cloth, compacting the two sides of the carbon fiber cloth by using a pressing block, and standing for later use;
d2) Preparation of carbon fiber cloth reinforced polyimide composite material part
C is to2Drying the prepared composite part in a high-temperature oven, firstly blowing and drying for 1-2h at normal temperature, then heating in a stepped manner, heating to 280-320 ℃, keeping the temperature for 50-70min, and dehydrating and cyclizing to obtain a carbon fiber cloth reinforced polyimide-based composite part;
e2) Preparation of high temperature carbonized materials
Will d2The composite member is placed in a reaction furnace with programmed temperature rise, and under the protection of inert gas, the temperature rises to 400-900 ℃ for carbonization treatment for 0.5-2h, and the N-doped carbon fiber cloth reinforced polyimide-based composite member is obtained.
The carbon fiber reinforced polyimide-based composite material comprises the following components in percentage by mass:
polyimide (I): 22 to 95 percent
Carbon fiber: 5 to 75 percent of
Coupling agent: 0 to 3 percent of
Wherein in said step A (a)1) The carbon fibers in (A) are preferably chopped fibers having different aspect ratiosCarbon fibers. The coupling agent is gamma-aminopropyltriethoxysilane (KH550) or gamma- (2, 3-glycidoxy) propyltrimethoxysilane (KH560) or gamma-methacryloxypropyltrimethoxysilane (KH570) or N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH 792).
Said step A (b)1)B(b2) The diamine in (b) is preferably one or a mixture of two of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine, m-phenylenediamine, dimethyldiphenylmethanediamine (DMMDA), 1, 3-bis (3-aminophenoxy) benzene (BAPB), 4, 4' -bisphenol a diphenyletherdiamine (BAPP), 4,4 '-bis (4-aminophenoxy) diphenylsulfone (BAPS), 4, 4' -bis (4-aminophenoxy) diphenylether (BAPE), diaminodiphenyl (methyl) ketone (DABP), 4,4 '-Diaminotriphenylamine (DATPA), 4, 4' -diaminodiphenylmethane (MDA), and diaminodiphenylsulfone (DDS).
Said step A (b)1)B(b2) The dianhydride(s) in (1) is preferably one or a mixture of two of pyromellitic dianhydride (PMDA), 3,3,4, 4-biphenyl tetracarboxylic dianhydride (BPDA), 4,4 ' -oxydiphthalic anhydride (ODPA), isomeric diphenyl sulfide dianhydride (TDPA), triphendiether tetracarboxylic dianhydride (HQDPA), Benzophenone Tetracarboxylic Dianhydride (BTDA), benzophenone tetracarboxylic dianhydride (BDTA), bisphenol A dianhydride (BPADA), monoether tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenyl sulfone tetracarboxylic dianhydride (DSDA).
Said step A (a)1)(b1)B(a2)(b2) The polar solvent in (1) is N, N '-dimethylacetamide (DMAc) or N, N' -Dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
Said step A (a)1) Adding a coupling agent for reaction, and controlling the temperature to be between room temperature and 50 ℃; the ultrasonic frequency is 20KHz-100 KHz; after adding dianhydride, stirring and reacting for 2-7h to obtain the composite solution with the mass percentage concentration of 10-40%.
Said step A (d)1) The mixed gel solution is preferably at least one of methanol, ethanol and water.
Said step A (d)1)B(d2) Heating in a baking oven in a step manner at a heating rate of 2-4 ℃/min from 40-50 ℃, heating to 85-120 ℃, keeping the temperature for 50-70min, heating to 185-215 ℃, keeping the temperature for 50minHeating to 280-320 ℃ for 50-70 min. The high-temperature carbonization temperature is controlled at 400-900 ℃.
The experimental operation process of the invention is controllable, and the implementation condition is mild. Provides a simple and feasible new method for preparing the polymer-based flexible electrode material. The fiber reinforced composite material part prepared by the method has controllable appearance and uniform product performance.
Has the advantages that:
1. the composite material prepared by the method has compact organic-inorganic structure, and a polymer can effectively coat the surface layer of the fiber and form a uniform and complete pore structure appearance, thereby effectively improving the specific surface area of the material.
2. Energy spectrum analysis shows that hybrid nitrogen atoms are effectively introduced into carbon atom lattices of the carbon material through high-temperature carbonization treatment, so that the catalytic activity of the material on electrode reaction is increased.
3. Due to the structural particularity of the fiber material and the excellent heat conduction characteristic, and the increase of the content of the carbon material in the system after the high-temperature carbonization treatment, the heat in the polymer matrix can be better diffused, and the thermal stability of the composite material is fundamentally improved.
4. Electrochemical performance tests show that the composite material after high-temperature treatment has good cycle life, stable electrochemical characteristics and good application prospect due to the effective formation of the surface active N of the material and the rapid transfer performance of electrolyte ions and electrons of the composite material endowed by the synergistic effect between the fibers and the polyimide material.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is an SEM photograph of example 1.
FIG. 2 is a N atom distribution diagram of example 1
FIG. 3 is an XPS N1 s spectrum of example 1
FIG. 4 is a cyclic voltammogram of the electrochemical test of example 1
FIG. 5 is a graph comparing the AC impedance of the composite material and the carbon fiber material of example 1
Detailed Description
Example 1
Firstly, 0.4g of chopped carbon fiber is weighed and put into an oven to be kept at the constant temperature of 100 ℃ for 4 hours. Then, the mixture was placed in a reactor containing 5g of a polar solvent DMAc, 0.004g of a coupling agent KH550 was added thereto, and the mixture was stirred at 20 ℃ and 20KHz for 0.5 hour. Adding 0.9573g of ODA into 3g of DMAc, carrying out ultrasonic stirring at the ultrasonic frequency of 40KHz, adding 1.0427g of dianhydride PMDA with the same molar amount as the ODA in 4 batches after the dianhydride PMDA is completely dissolved, continuously keeping the same temperature and the same frequency, carrying out ultrasonic stirring for 6 hours, and preparing the PAA solution with the mass fraction of 40%. Mixing the DMAc solution mixed with the carbon fibers with the PAA solution, continuously stirring to form a homogeneous phase to prepare a carbon fiber/PAA composite solution, and standing and defoaming for later use.
Coating the composite solution on a glass plate carrier, placing the glass plate in an ethanol/water gel solution (wherein the volume ratio of ethanol to water is 3:7) for gelation treatment, standing for 4h, placing the prepared composite membrane material in a forced air drying oven for drying at normal temperature for 1h, heating for imidization after the composite membrane material is basically dried, wherein the heating rate is 2.5 ℃/min (100 ℃ x 1h, 200 ℃ x 1h, 320 ℃ x 1h), and obtaining the carbon fiber reinforced polyimide composite membrane material. Wherein the mass ratio of the polyimide to the carbon fiber to the coupling agent is 83.2: 16.6: 0.2.
and (3) placing the composite membrane material in a tube furnace, heating to 800 ℃, keeping for 1h, and naturally cooling to obtain the N-doped carbon fiber reinforced composite membrane product.
In the embodiment, a large number of pore structures are formed in the composite system due to the gel replacement and high-temperature carbonization treatment, the specific surface area of the material is increased (as shown in figure 1), and the electric conductivity coefficient of the carbonized material reaches 1.32W/m.K after high-temperature carbonization decomposition. Meanwhile, hybrid nitrogen atoms (such as figures 2 and 3) are introduced into the carbon atom crystal lattice, so that the catalytic activity points of the material are increased. The specific surface area is increased, and C-N bonding is introduced, so that the specific capacitance of the composite material is obviously improved, the specific capacitance of the composite electrode in the embodiment is 140F/g, and due to high-temperature carbonization treatment, the carbonaceous material in the composite system is increased, so that the cyclic voltammetry curve still keeps an approximately rectangular shape without distortion even at a high scanning rate, and an efficient electric double layer structure is formed in the electrode (as shown in figure 4). The electrochemical impedance of the carbonized material electrode shows a small semicircular shape in a high-frequency region, so that the internal resistance effect of a polymer base is determined, and the limited diffusion Warburg or pseudo capacitance of the polymer corresponding to a linear peak is determined. Meanwhile, in a low frequency region, the straight line portion is more prone to have imaginary coordinates, and thus exhibits a better ion diffusion effect (see fig. 5). Overall, the composite electrode behaves close to a more ideal capacitor.
Example 2
Weighing 0.6528g of DDS at 25 ℃ and adding the DDS into a reactor filled with 3.5g of polar solvent DMF, carrying out ultrasonic stirring at an ultrasonic frequency of 20KHz, adding 0.8421g of dianhydride monomer BDTA which is equal to the DDS in molar amount in 3 batches after the DDS is completely dissolved, continuously keeping the same temperature and the same frequency for ultrasonic stirring, continuing for 4 hours, preparing a PAA solution with the mass fraction of 30%, and standing and defoaming for later use.
1.5g of carbon fiber cloth is suspended in the prepared PAA solution for 30min and then taken out. And spraying the redundant solution on two sides of the fiber cloth, and compacting the two sides. And then placing the composite material into a methanol/water gel solution (wherein the volume ratio of methanol to water is 5:5) for gelation treatment, standing for 5h, placing the prepared composite material workpiece into a forced air drying oven for drying at normal temperature for 1h, raising the temperature for imidization after the composite material workpiece is basically dried, wherein the heating rate is 4 ℃/min (120 ℃ x 70min, 210 ℃ x 70min and 280 ℃ x 70min), and obtaining the carbon fiber cloth reinforced polyimide composite film material. Wherein the mass ratio of the polyimide to the carbon fiber to the coupling agent is 50: 50: 0.
and (3) placing the composite membrane material in a tube furnace, heating to 500 ℃, keeping for 0.5h, and naturally cooling to obtain the N-doped carbon fiber reinforced composite membrane product.
The samples in the embodiment all show a relatively ideal porous structure, the polymer matrix is well coated on the surface layer of the fiber cloth, active N sites are successfully introduced into carbon lattices, and the activity of electrode reaction is increased. The heat conductivity coefficient of the carbonized composite material is 1.468W/m.K, the specific capacitance reaches 146F/g, and a higher electric double layer capacitance structure and a better ion diffusion effect are also reserved.
Example 3
Firstly, 0.0532g of chopped carbon fibers are weighed and put into an oven to be kept at the constant temperature of 150 ℃ for 1 h. Then the mixture is put into a reactor filled with 1g of polar solvent DMF, 0.0106g of coupling agent KH560 is added, and the mixture is stirred for 40min at 40 ℃ and the ultrasonic frequency of 80 KHz. 0.3809g of MDA is added into 9g of DMF, ultrasonic stirring is carried out, the ultrasonic frequency is 80KHz, after the mixture is completely dissolved, 0.6191g of dianhydride BTDA which is equal to the MDA in molar quantity is added into 6 batches, the ultrasonic stirring is continuously carried out at the same temperature and the same frequency for 5 hours, and the PAA composite solution with the mass fraction of 10% is prepared. And mixing the DMF solution mixed with the carbon fibers with the PAA solution, continuously stirring to form a homogeneous phase to prepare a carbon fiber/PAA composite solution, and standing and defoaming for later use.
Coating the composite solution on a glass plate carrier, placing the glass plate in a gel solution of ethanol for gelation treatment, standing for 8h, placing the prepared composite membrane material in a forced air drying oven for drying at normal temperature for 1.5h, and heating for imidization after the composite membrane material is basically dried, wherein the heating rate is 3 ℃/min (90 ℃ x 50min, 215 ℃ x 70min, 290 ℃ x 70min), so as to obtain the carbon fiber reinforced polyimide composite membrane material. Wherein the mass ratio of the polyimide to the carbon fiber to the coupling agent is 94:5: 1.
And (3) placing the composite membrane material in a tube furnace, heating to 500 ℃, keeping for 2h, and naturally cooling to obtain the N-doped carbon fiber reinforced composite membrane product.
The samples in the embodiment all show a relatively ideal porous structure, the polymer matrix is well coated on the surface layer of the carbon chopped fiber, active N sites are successfully introduced into carbon lattices, and the activity of electrode reaction is increased. The thermal conductivity coefficient of the carbonized composite material is 1.211W/m.K, the specific capacitance reaches 104F/g, and a higher electric double layer capacitance structure and a better ion diffusion effect are also reserved.
Example 4
Weighing 0.2983g of p-phenylenediamine at 30 ℃ and adding the p-phenylenediamine into a reactor filled with 1.7106g of polar solvent NMP, carrying out ultrasonic stirring at the ultrasonic frequency of 50KHz, adding 0.8421g of dianhydride monomer BPDA which is equal to the p-phenylenediamine in molar amount in 5 batches after the p-phenylenediamine is completely dissolved, continuously keeping the same temperature and the same frequency for ultrasonic stirring, keeping the ultrasonic stirring for 5.5 hours to prepare a PAA solution with the mass fraction of 40%, and standing and defoaming for later use.
3.4212g of carbon fiber cloth is suspended in the prepared PAA solution for 30min and then taken out. And spraying the redundant solution on two sides of the fiber cloth, and compacting the two sides. And then placing the composite material into a methanol gel solution for gelation treatment, standing for 9h, placing the prepared composite material workpiece into a forced air drying oven for drying at normal temperature for 2h, raising the temperature for imidization after the composite material workpiece is basically dried, wherein the raising rate is 4 ℃/min (85 ℃ x 70min, 200 ℃ x 60min, 310 ℃ x 65min), and obtaining the carbon fiber cloth reinforced polyimide composite film material. Wherein the mass ratio of the polyimide to the carbon fiber to the coupling agent is 25:75: 0.
And (3) placing the composite membrane material in a tube furnace, heating to 900 ℃, keeping for 1.5h, and naturally cooling to obtain the N-doped carbon fiber reinforced composite membrane product.
The samples in the embodiment all show a relatively ideal porous structure, the polymer matrix is well coated on the surface layer of the carbon fiber cloth, active N sites are successfully introduced into carbon lattices, and the activity of electrode reaction is increased. The heat conductivity coefficient of the carbonized composite material is 1.327W/m.K, the specific capacitance reaches 128F/g, and a higher electric double layer capacitance structure and a better ion diffusion effect are also reserved.
Example 5
Firstly, 4.2824g of chopped carbon fiber is weighed and put into an oven to be kept at the constant temperature of 120 ℃ for 3 h. Then, the mixture was put into a reactor containing 13.3604g of DMF, and 0.1713g of KH792 as a coupling agent was added thereto, and the mixture was stirred at 30 ℃ and 100KHz as an ultrasonic frequency for 1 hour. Adding 0.7155g of BAPP into 3.7686g of DMF, carrying out ultrasonic stirring at an ultrasonic frequency of 100KHz, adding 0.5407g of dianhydride ODPA with the same molar amount as BAPP into each 6 batches after the dianhydride ODPA is completely dissolved, continuously carrying out ultrasonic stirring at the same temperature and the same frequency for 7 hours to prepare a PAA solution with the mass fraction of 25%. Mixing the DMF solution mixed with the carbon chopped fibers with the PAA solution, continuously stirring to be homogeneous to prepare a carbon fiber/PAA composite solution, and standing and defoaming for later use.
And coating the composite solution on a glass plate carrier, placing the glass plate in a water gel solution for gelation treatment, standing for 12h, placing the prepared composite membrane material in a forced air drying oven for drying at normal temperature for 1.5h, and heating for imidization after the composite membrane material is basically dried, wherein the heating rate is 4 ℃/min (85 ℃ x 70min, 185 ℃ x 50min, 280 ℃ x 70min), so as to obtain the carbon fiber reinforced polyimide composite membrane material. Wherein the mass ratio of the polyimide to the carbon fiber to the coupling agent is 22:75: 3.
And (3) placing the composite membrane material in a tube furnace, heating to 600 ℃, keeping for 2h, and naturally cooling to obtain the N-doped carbon fiber reinforced composite membrane product.
The samples in the embodiment all show a relatively ideal porous structure, the polymer matrix is well coated on the surface layer of the carbon chopped fiber, active N sites are successfully introduced into carbon lattices, and the activity of electrode reaction is increased. The thermal conductivity coefficient of the carbonized composite material is 1.401W/m.K, the specific capacitance reaches 131F/g, and a higher electric double layer capacitance structure and a better ion diffusion effect are also reserved.
Claims (8)
1. A fiber reinforced polyimide-based composite material is characterized in that the fiber reinforced polyimide-based composite material comprises the following components in percentage by mass of the total mass of the composite material:
polyimide (I): 22 to 95 percent
Carbon fiber: 5 to 75 percent of
Coupling agent: 0 to 3 percent; the carbon fiber is carbon chopped fiber or carbon fiber cloth.
2. The fiber-reinforced polyimide-based composite material according to claim 1, wherein the coupling agent is γ -aminopropyltriethoxysilane or γ - (2, 3-glycidoxy) propyltrimethoxysilane or γ -methacryloxypropyltrimethoxysilane or N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane (ETO).
3. A method for preparing the fiber reinforced polyimide-based composite material according to claim 1, comprising the following specific steps:
A. preparation of carbon chopped fiber reinforced polyimide composite material
a1) Pretreatment of raw materials:
firstly, placing carbon chopped fibers into an oven to keep constant temperature treatment; then putting the chopped fibers into a reactor filled with a polar solvent, adding a coupling agent, controlling the temperature and carrying out ultrasonic stirring;
b1) Preparation of Polyamic acid (PAA) solution
Preparing a PAA solution with the mass concentration of 10-40%;
c1) Preparation of carbon chopped fiber-PAA composite solution
A is to1) Mixing the solution with b1) Mixing the PAA solution, and continuously stirring to obtain a homogeneous phase to obtain a carbon chopped fiber-PAA composite solution;
d1) Preparation of carbon chopped fiber reinforced polyimide composite material part
C is to1) The composite solution prepared in the step (1) is suspended on a flat carrier, then the flat carrier is placed in a gel mixed solution for gelation, and a composite flat membrane material piece with a porous appearance is obtained after 1-12 hours; putting the workpiece into a high-temperature oven for drying treatment, firstly carrying out air blast drying at normal temperature for 1-2h, then carrying out step heating, heating to 280-320 ℃, keeping the temperature for 50-70min, and carrying out dehydration cyclization to obtain a carbon chopped fiber reinforced polyimide-based composite part;
e1) Preparation of high temperature carbonized materials
Will d1The composite part is placed in a temperature programmed reaction furnace, and is heated to 900 ℃ under the protective atmosphere to carry out carbonization treatment, so as to obtain the N-doped carbon chopped fiber reinforced polyimide-based composite material;
B. preparation of carbon fiber cloth reinforced polyimide-based composite material part
a2) Pretreatment of raw materials:
firstly, putting carbon fiber cloth into an oven to be processed at a constant temperature; then putting the chopped fibers into a reactor filled with a polar solvent, controlling the temperature, ultrasonically stirring, and standing for later use;
b2) Preparation of Polyamic acid PAA solutionPrepare for
Preparing a PAA solution with the mass solid content of 10-40%;
c2) Preparation of PAA coated carbon fiber cloth composite part
A is to2) In the carbon fiber cloth is suspended in the b2) Taking out the PAA solution for 10-30 min; uniformly spraying the residual PAA solution on two sides of the carbon fiber cloth, compacting the two sides of the carbon fiber cloth by using a pressing block, and standing for later use;
d2) Preparation of carbon fiber cloth reinforced polyimide composite material part
C is to2) Drying the prepared composite part in a high-temperature oven, firstly blowing and drying for 1-2h at normal temperature, then heating in a stepped manner, heating to 280-320 ℃, keeping the temperature for 50-70min, and dehydrating and cyclizing to obtain a carbon fiber cloth reinforced polyimide-based composite part;
e2) Preparation of high temperature carbonized materials
Will d2) The composite member is placed in a temperature programmed reaction furnace, and is carbonized at the high temperature of 500-900 ℃ under the protective atmosphere to obtain the N-doped carbon fiber cloth reinforced polyimide-based composite material.
4. Method according to claim 3, characterized in that step d is carried out1) The gel mixed solution in (1) is at least one of methanol, ethanol or water.
5. Method according to claim 3, characterized in that step a1) And a2) The temperature of the drying oven is 100-150 ℃, and the constant temperature is kept for 1-4 h; step a1) And a2) Adding coupling agent, controlling temperature at 20-50 deg.C and frequency at 20KHz-100KHz, and ultrasonic stirring for 0.5-1 h.
6. Method according to claim 3, characterized in that step a2) The medium standing time is 5-9 h.
7. Method according to claim 3, characterized in that step d is carried out1) And step d2) The step heating is as follows: the heating rate is 2-4 ℃/min, the temperature is raised from 40-50 ℃, the temperature is raised to 85-120 ℃, the constant temperature is kept for 50-70min, the temperature is raised to 185-320 ℃, the constant temperature is kept for 50-70min, and the temperature is raised to 280-320 ℃ and the constant temperature is kept for 50-70 min.
8. Method according to claim 3, characterized in that step e is carried out1) And step e2) The protective atmosphere in the method is nitrogen, and the carbonization time is controlled to be 0.5-2 h.
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| CN115895003A (en) * | 2022-10-18 | 2023-04-04 | 南京工业大学 | Ablation-resistant polyimide-based structure gradient composite material and preparation method thereof |
| CN116375472A (en) * | 2023-02-28 | 2023-07-04 | 安徽国风新材料股份有限公司 | Super-thick polyimide-based graphite film and preparation method thereof |
| CN117325485A (en) * | 2023-11-30 | 2024-01-02 | 乌镇实验室 | Carbon fiber reinforced polyamide composite material for wind power blade and preparation method thereof |
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| CN115121127A (en) * | 2022-06-16 | 2022-09-30 | 中国科学院苏州纳米技术与纳米仿生研究所 | Aerogel confinement solid-liquid composite membrane for extracting uranium from seawater and preparation method and application thereof |
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| CN116375472A (en) * | 2023-02-28 | 2023-07-04 | 安徽国风新材料股份有限公司 | Super-thick polyimide-based graphite film and preparation method thereof |
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| CN117325485B (en) * | 2023-11-30 | 2024-03-08 | 乌镇实验室 | Carbon fiber reinforced polyamide composite material for wind power blade and preparation method thereof |
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