CN115693021A - Polyimide fiber/aerogel composite membrane and preparation method thereof - Google Patents
Polyimide fiber/aerogel composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polyimide fiber/aerogel composite membrane and a preparation method thereof, the method comprises the steps of uniformly mixing an aromatic dianhydride monomer and an aromatic diamine monomer in an organic solvent to obtain a reaction solution, and carrying out condensation polymerization reaction to obtain a polyamic acid solution; adding a 3-aminopropyltriethoxysilane crosslinking agent into the polyamic acid solution for chemical crosslinking, then adding a dehydrating agent and a catalyst, and controlling the proportion to obtain a polyamic acid-polyimide solution; coating the polyimide solution on the surface of a polyimide electrostatic spinning membrane to obtain a wet gel composite film, and then aging; and (3) placing the aged film in an organic solvent for solvent exchange, then drying at normal pressure, and finally performing thermal imidization treatment to obtain the polyimide fiber/aerogel composite film. The composite diaphragm has the average pore diameter of 100-200 nanometers, high porosity, good mechanical property, high wettability and high temperature resistance.
Description
Technical Field
The invention belongs to the technical field of membrane materials and batteries, and relates to a polyimide fiber/aerogel composite membrane and a preparation method thereof.
Background
Lithium ion batteries are now widely used in the field of electrical energy storage for mobile electronic devices, electric vehicles, and the like. While the lithium ion battery benefits mankind, the lithium ion battery also has potential danger, and frequent combustion and explosion accidents of the lithium ion battery bring great threat to the life and property safety of people. The diaphragm is used as a physical barrier between the anode and the cathode, internal short circuit is avoided, meanwhile, smooth passing of lithium ions can be guaranteed, the diaphragm plays a key role in application of the lithium battery, and safety and electrochemical performance of the battery are greatly influenced. Most separators in commercial use today are polyolefin materials, including polypropylene and polyethylene, which have high flammability and low thermal stability. Since the conventional polyolefin-based separator is easily thermally shrunk, the rapid reduction in the size of the separator may cause a short circuit inside the battery, which may instantaneously release a large amount of heat and even directly cause explosion of the lithium battery. Therefore, it is necessary and urgent to develop an advanced separator capable of satisfying all requirements of lithium batteries and having high safety and high electrochemical properties.
Polyimide (PI) is a high polymer material with good thermal stability and mechanical property. The high temperature resistance of the composite material reaches more than 400 ℃, and the long-term use temperature range is between-200 and 300 ℃. At present, the method for producing the polyimide-based battery diaphragm mainly comprises electrostatic spinning. Common electrospun polyimide membranes typically have large and non-uniform pore sizes (about 2 microns), which can lead to self-discharge and dendrite growth problems; the polyimide aerogel material has the advantages of nano-scale pore size structure, high porosity, large specific surface area, uniform pore size and the like, but the mechanical property of a pure polyimide aerogel film is generally poor, and the requirement of a battery diaphragm is difficult to meet. The composite membrane can be compounded with the electrostatic spinning fiber membrane to effectively combine the advantages of the electrostatic spinning fiber membrane and the electrostatic spinning fiber membrane, and the composite membrane with good mechanical property and small and uniform pore diameter is obtained.
Disclosure of Invention
The invention aims to: aiming at the problems and the defects in the prior art, the invention provides a preparation method and application of a polyimide fiber/aerogel composite membrane, wherein the mechanical property, the micro-pore structure regulation, the porosity, the pore size distribution, the electrolyte absorption and retention and the like of the composite membrane are greatly improved.
In a first aspect of the present invention, there is provided a method for preparing a polyimide fiber/aerogel composite membrane, the method comprising the steps of:
(1) Dissolving a diamine monomer in a reaction solvent, introducing nitrogen, and adding a dianhydride monomer under the condition of stirring in an ice-water bath to prepare a polyamic acid solution;
(2) Adding a silane cross-linking agent into the polyamic acid solution to carry out chemical cross-linking, and then adding an imidization reagent to obtain a polyamic acid-polyimide solution;
(3) Coating the polyamic acid-polyimide solution on the surface of a polyimide fiber membrane (namely a polyimide electrostatic spinning membrane) to obtain a polyimide wet gel composite membrane, and then aging;
(4) Placing the aged polyimide wet gel composite membrane in an organic solvent for solvent exchange, and then drying;
(5) And finally, imidizing to obtain the polyimide fiber/aerogel composite membrane.
In one embodiment, in step (1), the molar ratio of diamine monomer to dianhydride monomer is 1: 1.01 to 1: 1.10, preferably 1: 1.05.
In one embodiment, the mass concentration of the polyamic acid solution in the step (1) is 3% to 15%, preferably 7%.
In one embodiment, in the step (1), the diamine monomer is an aromatic diamine monomer, and includes at least one of p-phenylenediamine, benzidine, diaminodiphenyl ether, and diaminobenzophenone, and preferably diaminodiphenyl ether.
In one embodiment, in the step (1), the dianhydride monomer is an aromatic dianhydride monomer, and includes at least one of pyromellitic anhydride, pyromellitic dianhydride, hexafluoro dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride, and preferably pyromellitic dianhydride.
In one embodiment, in the step (1), the reaction solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and preferably N, N-dimethylacetamide.
In one embodiment, in step (1), the dianhydride monomer is added in portions. Preferably, the addition is carried out in three portions.
In one embodiment, in the step (2), the silane crosslinking agent includes at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, and 3-aminopropylmethyldimethoxysilane.
In one embodiment, in step (2), the molar ratio of the silane crosslinking agent to the diamine monomer is 1: 0.5 to 3, preferably 1: 1.
In one embodiment, in step (2), the imidizing agent includes a catalyst and a dehydrating agent.
In one embodiment, the catalyst comprises at least one of pyridine, picoline and triethylamine, and the molar ratio of the catalyst to the diamine monomer is 1: 0.5-3, preferably 1: 1.
In one embodiment, the dehydrating agent is at least one of acetic anhydride, acetyl chloride, thionyl chloride, phosphorus halide, an organosilicon compound, dicyclohexylcarbodiimide.
In one embodiment, the molar ratio of the dehydrating agent to the diamine monomer is 1: 0.5 to 3, preferably 1: 1.
In one embodiment, in the step (3), the gel is aged for 30s-5min.
In one embodiment, the gel is aged in step (3) for 30s-5min, preferably 30s.
In one embodiment, the solvent used for solvent exchange includes at least one of methanol, ethanol, acetone, cyclohexane, and n-hexane.
In one embodiment, in the step (4), the solvents selected for solvent exchange are ethanol and n-hexane, which are respectively soaked for 4-24h, preferably 12h.
In one embodiment, in the step (4), the drying is to remove the solvent in an oven.
In one embodiment, the drying parameter in step (4) is 30-80 ℃ under normal pressure.
In one embodiment, in the step (5), the thermal imidization is performed by performing a stepwise temperature rise, that is, performing a stepwise temperature rise on the composite film by using a tube furnace or a muffle furnace, to complete the imidization process.
In one embodiment, the temperature nodes of the staged heating are: the heating speed is 5 ℃/min at 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃, and the heat preservation time of each temperature node is 1h.
In a second aspect, the invention provides a polyimide fiber/aerogel composite membrane prepared by the technical method.
In one embodiment, the polyimide fiber/aerogel composite membrane has an average pore size of 100 to 200 nm.
In a third aspect, the invention provides the technical method and the application of the polyimide fiber/aerogel composite prepared by the technical method, and the polyimide fiber/aerogel composite is applied to the field of battery separators.
In one embodiment, the invention provides a battery separator, which is the polyimide fiber/aerogel composite membrane described in the above technical scheme.
Compared with the prior art, the invention has the beneficial effects that:
1. the polyimide fiber/aerogel composite membrane disclosed by the invention adopts a sol-gel method to generate aerogel on the surface of a spinning membrane, so that the pores are uniform, the average pore diameter is smaller, and the method is different from the traditional electrostatic spinning method; and has high wettability and high temperature resistance.
2. The polyimide fiber/aerogel composite membrane prepared by the invention uses the electrostatic spinning membrane as a framework, has better mechanical properties compared with a pure aerogel membrane, has good tensile strength and strain force, and greatly improves the safety performance.
3. The cross-linking agent used in the invention is 3-aminopropyl triethoxysilane, contains silicon element, has higher thermal stability and better insulation property, and is more suitable for battery separators.
4. The invention uses the normal pressure drying mode to prepare the aerogel structure, and is more suitable for the large-scale industrialized production of the battery diaphragm.
Drawings
FIG. 1 is a scanning electron micrograph of a polyimide fiber/aerogel composite film according to example 1.
FIG. 2 is a graph of the stress-strain tensile properties of the polyimide fiber/aerogel composite membrane of example 1 and the polyimide fiber membrane of comparative example 1.
FIG. 3 is a graph showing the results of thermogravimetric testing of the polyimide fiber/aerogel composite membrane of example 1 and the polyimide fiber membrane of comparative example 1.
Fig. 4 is a graph showing the results of the electrolyte absorption and retention tests of the polyimide fiber/aerogel composite membrane of example 1 and the polyimide fiber membrane of comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The sources of reagents used in the examples of the present invention are commercially available, except where otherwise specified.
The present invention provides the figure of the characterization test result of embodiment 1, and other embodiments all use the same characterization test method, so that those skilled in the art can directly and unambiguously determine the content of the embodiment of the present invention through the characterization test method provided by the present invention, and details are not repeated herein.
Example 1: preparation of polyimide fiber/aerogel composite membrane
(1) 39.71g (0.456 mol) of N, N-dimethylacetamide is weighed as a reaction solvent and added into a three-neck flask, a stirring motor is turned on to stir, inert gas is continuously introduced, and the three-neck flask is placed in an ice-water bath. Then adding 1.00g (0.005 mol) of diamine monomer 4,4' -diaminodiphenyl ether, and stirring to completely dissolve the diamine monomer; 1.09g (0.005 mol) of pyromellitic dianhydride is added into the obtained solution in three batches, and the stirring is continued at low temperature of ice-water bath until yellow uniform viscous polyamic acid is obtained, wherein the mass concentration of the polyamic acid solution is 5 percent.
(2) Adding 1.11g (0.005 mol) of 3-aminopropyltriethoxysilane into the polyamic acid solution obtained in the step (1), stirring at low temperature for 30min, and carrying out chemical crosslinking; then, 0.51g (0.005 mol) of acetic anhydride as a dehydrating agent and 0.50g (0.005 mol) of triethylamine as a catalyst were added thereto, and the mixture was stirred at a low temperature for 30 minutes to obtain a yellow modified polyamic acid/polyimide solution.
(3) And (3) uniformly coating the gel prepared in the step (2) on a polyimide fiber membrane, standing and aging for 30s, soaking in ethanol for 12h, transferring to n-hexane for soaking for 12h, and performing solvent exchange.
(4) And (4) drying the wet gel composite membrane obtained in the step (3) in an oven at the room temperature of 30 ℃ for 30min under normal pressure to finish the drying of the wet gel composite membrane.
(5) And (3) carrying out step heating on the composite membrane obtained in the step (4) by using a muffle furnace, wherein the temperature nodes are 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃ in sequence, the heating speed is 5 ℃/min, and each temperature node is kept for 1h.
Example 2: preparation of polyimide fiber/aerogel composite membrane
(1) 39.71g (0.456 mol) of N, N-dimethylacetamide is weighed as a reaction solvent, added into a three-neck flask, a stirring motor is turned on for stirring, inert gas is continuously introduced, and the three-neck flask is placed in an ice-water bath. Then adding 1.00g (0.005 mol) of diamine monomer 4,4' -diaminodiphenyl ether, and stirring to completely dissolve the diamine monomer; the dianhydride monomer was added to the resulting solution in three portions to give 1.09g (0.005 mol) of pyromellitic dianhydride. And (3) continuously stirring in the ice-water bath at a low temperature until yellow uniform viscous polyamic acid is obtained, wherein the mass concentration of the polyamic acid solution is 5%.
(2) Adding 0.55g (0.0025 mol) of 3-aminopropyltriethoxysilane into the polyamic acid solution obtained in the step (1), and stirring at low temperature for 30min; carrying out chemical crosslinking; then, 0.51g (0.005 mol) of acetic anhydride as a dehydrating agent and 0.50g (0.005 mol) of triethylamine as a catalyst were added thereto, and the mixture was stirred at a low temperature for 30 minutes to obtain a yellow polyamic acid/polyimide solution.
(3) And (3) uniformly coating the gel prepared in the step (2) on a polyimide fiber membrane, standing and aging for 30s, then soaking in ethanol for 12h, then transferring to n-hexane for soaking for 12h, and performing solvent exchange.
(4) And (4) drying the wet gel composite membrane obtained in the step (3) in an oven at the room temperature of 30 ℃ for 30min under normal pressure to finish the drying of the wet gel composite membrane.
(5) And (3) carrying out step heating on the composite membrane obtained in the step (4) by using a muffle furnace, wherein the temperature nodes are 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃ in sequence, the heating speed is 5 ℃/min, and each temperature node is kept for 1h.
Example 3: preparation of polyimide fiber/aerogel composite membrane
(1) 18.81g (0.216 mol) of N, N-dimethylacetamide as a reaction solvent was weighed into a three-necked flask, and the three-necked flask was placed in an ice-water bath with stirring by turning on a stirring motor and continuously introducing an inert gas. Then adding 1.00g (0.005 mol) of diamine monomer 4,4' -diaminodiphenyl ether, and stirring to completely dissolve the diamine monomer; the dianhydride monomer (1.09 g, 0.005 mol) was added to the resulting solution in three portions. And (3) continuously stirring in the ice-water bath at a low temperature until yellow uniform viscous polyamic acid is obtained, wherein the mass concentration of the polyamic acid solution is 10%.
(2) Adding 0.55g (0.0025 mol) of 3-aminopropyltriethoxysilane into the polyamic acid solution obtained in the step (1), and stirring at low temperature for 30min; carrying out chemical crosslinking; then, 0.51g (0.005 mol) of acetic anhydride as a dehydrating agent and 0.50g (0.005 mol) of triethylamine as a catalyst were added thereto, and the mixture was stirred at a low temperature for 30 minutes to obtain a yellow polyamic acid/polyimide solution.
(3) And (3) uniformly coating the gel prepared in the step (2) on a polyimide fiber membrane, standing and aging for 30s, then soaking in ethanol for 12h, then transferring to n-hexane for soaking for 12h, and performing solvent exchange.
(4) And (4) drying the wet gel composite membrane obtained in the step (3) in an oven at the room temperature of 30 ℃ for 30min under normal pressure to finish the drying of the wet gel composite membrane.
(5) And (3) carrying out step heating on the composite membrane obtained in the step (4) by using a muffle furnace, wherein the temperature nodes are 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃ in sequence, the heating speed is 5 ℃/min, and each temperature node is kept for 1h.
Example 4: preparation of polyimide fiber/aerogel composite membrane
(1) 39.71g (0.456 mol) of N, N-dimethylacetamide is weighed as a reaction solvent, added into a three-neck flask, a stirring motor is turned on for stirring, inert gas is continuously introduced, and the three-neck flask is placed in an ice-water bath. Then adding 1.00g (0.005 mol) of diamine monomer 4,4' -diaminodiphenyl ether, and stirring to completely dissolve the diamine monomer; the dianhydride monomer (1.09 g, 0.005 mol) was added to the resulting solution in three portions. Stirring is continued at low temperature in the ice-water bath until yellow uniform viscous polyamic acid is obtained, and the mass concentration of the polyamic acid solution is 10%.
(2) Adding 0.55g (0.0025 mol) of 3-aminopropyltriethoxysilane into the polyamic acid solution obtained in the step (1), and stirring at low temperature for 30min; carrying out chemical crosslinking; then, 0.51g (0.005 mol) of acetic anhydride as a dehydrating agent and 0.50g (0.005 mol) of triethylamine as a catalyst were added thereto, and the mixture was stirred at a low temperature for 30 minutes to obtain a yellow polyamic acid/polyimide solution.
(3) And (3) uniformly coating the gel prepared in the step (2) on a polyimide fiber membrane, standing and aging for 30s, then soaking in ethanol for 12h, then transferring to n-hexane for soaking for 12h, and performing solvent exchange.
(4) And (4) drying the wet gel composite membrane obtained in the step (3) in an oven at room temperature of 60 ℃ for 30min under normal pressure to finish the drying of the wet gel composite membrane.
(5) And (3) carrying out step heating on the composite membrane obtained in the step (4) by using a muffle furnace, wherein the temperature nodes are 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃ in sequence, the heating speed is 5 ℃/min, and each temperature node is kept for 1h.
Comparative example 1: polyimide fiber membrane
This comparative example was compounded without using a polyimide aerogel and was a pure polyimide electrospun membrane.
Experimental example: battery performance test of polyimide fiber/aerogel composite membrane
As shown in fig. 1, which is a scanning electron microscope image of the polyimide fiber/aerogel composite film in example 1, the composite film to be tested is adhered to a sample stage by using a conductive adhesive tape, and the surface of the sample is subjected to gold spraying treatment, so that it can be obviously observed that the composite film has a smaller pore size. Through statistical analysis on the pore size distribution result of a scanning electron microscope, the pore size distribution of the polyimide fiber/aerogel composite membrane obtained in the embodiment of the present application is 100-200 nm, and it should be noted that the "pore size distribution of the composite membrane" referred to in the present application refers to the average pore size of the aerogel layers on both sides of the composite membrane. Compared with the products obtained by the traditional electrostatic spinning method and the comparative example 1, the product has smaller pore size distribution.
As shown in fig. 2, which is a tensile property test chart of the polyimide fiber/aerogel composite membrane in example 1, the tensile strength of example 1 exceeds 40MPa, and the strain reaches 49%, which is greatly improved compared with the polyimide fiber membrane in comparative example 1.
As shown in fig. 3, which is a thermogravimetric test result of the polyimide fiber/aerogel composite membrane of example 1, it can be seen that: the prepared polyimide fiber/aerogel composite membrane begins to generate a thermal weight loss phenomenon at 500 ℃, which shows that the polyimide fiber/aerogel composite membrane has higher use safety under a high-temperature condition, and compared with the polyimide fiber membrane of the comparative example 1, the polyimide fiber/aerogel composite membrane has great improvement.
As shown in fig. 4, which is a graph of the results of the electrolyte absorption and retention tests of the polyimide fiber/aerogel composite membrane of example 1, it can be seen that: the prepared polyimide fiber/aerogel composite membrane can absorb more than 550% of electrolyte by mass, and the retention of the electrolyte is still more than 70% after standing for 600min, which shows that the polyimide fiber/aerogel composite membrane has good affinity with the electrolyte, and is greatly improved compared with the polyimide fiber membrane (namely the fiber membrane in fig. 4) in comparative example 1.
It should be noted that, in examples 2 to 4, the same method as in example 1 can also be used to perform performance testing on the product, and all the technical effects similar to those in example 1 are obtained, which is not described herein again.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A preparation method of a polyimide fiber/aerogel composite membrane is characterized by comprising the following steps:
(1) Dissolving a diamine monomer in a reaction solvent, introducing nitrogen, and adding a dianhydride monomer under the condition of stirring in an ice-water bath to prepare a polyamic acid solution;
(2) Adding a 3-aminopropyl triethoxysilane cross-linking agent into the polyamic acid solution for chemical cross-linking, and then adding an imidization reagent to obtain a polyamic acid-polyimide solution;
(3) Coating the polyamic acid-polyimide solution on a polyimide fiber membrane to obtain a polyimide wet gel composite membrane, and then aging;
(4) Placing the aged polyimide wet gel composite membrane in an organic solvent for solvent exchange, and then drying;
(5) And finally, performing thermal imidization to obtain the polyimide fiber/aerogel composite membrane.
2. The method for preparing a polyimide fiber/aerogel composite membrane according to claim 1, wherein the diamine monomer in step (1) is an aromatic diamine monomer comprising at least one of p-phenylenediamine, benzidine, diaminodiphenyl ether, or diaminobenzophenone;
the dianhydride monomer in the step (1) is an aromatic dianhydride monomer and comprises at least one of pyromellitic dianhydride, hexafluoro dianhydride, pyromellitic dianhydride or benzophenone tetracarboxylic dianhydride;
the reaction solvent in the step (1) is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
3. The method for preparing a polyimide fiber/aerogel composite membrane according to claim 1, wherein the molar ratio of the diamine monomer to the dianhydride monomer in step (1) is 1: 1.01 to 1: 1.10.
4. The method for preparing a polyimide fiber/aerogel composite membrane according to claim 1, wherein the mass concentration of the polyamic acid solution in the step (1) is 3% to 15%.
5. The method for preparing a polyimide fiber/aerogel composite membrane according to claim 1, wherein in the step (2), the silane crosslinking agent comprises at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane and 3-aminopropylmethyldimethoxysilane crosslinking agent, and the molar ratio of the silane crosslinking agent to the diamine monomer is 1: 0.5-3.
6. The method for preparing a polyimide fiber/aerogel composite film according to claim 1, wherein in the step (2), the imidizing agent comprises a catalyst and a dehydrating agent,
the catalyst comprises at least one of pyridine, picoline and triethylamine,
the molar ratio of the catalyst to the diamine monomer is 1: 1;
the dehydrating agent comprises at least one of acetic anhydride, acetyl chloride, thionyl chloride, halide of phosphorus, an organic silicon compound and dicyclohexylcarbodiimide,
the catalyst is preferably triethylamine, and the dehydrating agent is preferably acetic anhydride;
the mol ratio of the dehydrating agent to the catalyst to the diamine monomer is (0.5-3) to 1, preferably 1: 1.
7. The preparation method of the polyimide fiber/aerogel composite membrane according to claim 1, wherein in the step (3), the polyimide solution is coated on the surface of the polyimide spinning membrane, and the polyimide spinning membrane is left to stand and age for 0.5-5min to obtain a polyimide wet gel film;
placing the aged film in an organic solvent for solvent exchange, wherein the exchanged solvent comprises at least one of methanol, ethanol, acetone, cyclohexane and n-hexane;
the drying parameter in the step (4) is 30-80 ℃ under the normal pressure condition;
in the step (5), the thermal imidization is performed by stage heating, and the temperature nodes of the stage heating are as follows in sequence: the temperature is 50 ℃, 100 ℃, 150 ℃, 200 ℃ and 300 ℃, the heating speed is 5 ℃/min, and each temperature point is kept for 1h.
8. A polyimide fiber/aerogel composite membrane, characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. The polyimide fiber/aerogel composite membrane according to claim 8, wherein the average pore size of the polyimide fiber/aerogel composite membrane is 100 to 200 nm.
10. Use of the polyimide fiber/aerogel composite membrane according to any one of claims 1 to 7 or the polyimide fiber/aerogel composite membrane according to claim 8 or 9 in the field of battery separators.
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