CN114773676A - Organic montmorillonite and polyimide composite porous membrane and preparation method and application thereof - Google Patents
Organic montmorillonite and polyimide composite porous membrane and preparation method and application thereof Download PDFInfo
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
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- 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
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Abstract
The invention relates to an organic montmorillonite and polyimide composite porous membrane, a preparation method and application thereof. The preparation method of the organic montmorillonite/polyimide composite porous membrane comprises the following steps: firstly, carrying out intercalation reaction on montmorillonite to obtain organic montmorillonite; adding organic montmorillonite and polyimide into an organic solvent, heating and stirring to obtain an organic montmorillonite/polyimide mixed membrane casting solution; and dripping the casting film on a release film, forming a film by blade coating, and soaking the film in a coagulating bath to solidify the film to obtain the organic montmorillonite/polyimide composite porous film. The organic montmorillonite/polyimide composite porous membrane obtained by the preparation method is used as a lithium ion battery diaphragm, and can effectively improve the electrochemical performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of high polymer material preparation, and particularly relates to a material of a lithium ion battery diaphragm, a preparation method and application.
Background
Gases generated by the combustion of fossil energy are also easy to cause greenhouse effect and pollution to the environment, so that the use of pollution-free and renewable energy is an effective way to replace fossil energy. The lithium ion battery is a simple and efficient device with high energy storage, and the diaphragm is a key component of the lithium ion battery and plays an important role in stability and safety of the battery. Polyolefin separators are currently commercially available materials, but have low thermal stability and poor wettability, and thus it is important to develop a new material having high performance.
The polyimide has the performances of long charge-discharge cycle life, moderate mechanical strength, good electrical insulation performance, self-extinguishing capability and the like, and can be used in the aspects of aerospace, electrical and electronic, precision machinery and the like. In recent years, polyimide has been widely used in the fields of battery materials, paints, liquid crystal displays, and the like, and secondly, polyimide contains a rigid aromatic skeleton to provide high thermal stability, and contains an imide ring having polarity and a nitrogen atom having a lone electron pair, so that the polyimide material has good affinity with a polar solvent as a thin film. Polyimide is used as a lithium ion battery separator due to its high performance. The general composite material has better performance than a pure polymer material, however, at present, most of the fillers are inorganic materials and have stronger interface effect with a polymer matrix membrane.
Disclosure of Invention
The invention aims to develop a preparation method of an organic montmorillonite and polyimide composite porous membrane aiming at the serious interface effect of the current inorganic filler.
In order to achieve the purpose of the invention, the technical scheme of the invention is as follows: the organic montmorillonite is prepared by intercalating and modifying montmorillonite, and inserting organic alkyl chain cations into interlayer of montmorillonite to change the interlayer environment from oleophobic to oleophilic, thereby improving the compatibility with organic polymers. In addition, the nano silicate of the organic montmorillonite and the carbonate solvent in the electrolyte have good affinity, so that the affinity of the diaphragm and the electrolyte can be improved, and further the ionic conductivity and the cycle performance of the lithium ion battery diaphragm are improved. The invention specifically adopts the following technical scheme:
a preparation method of an organic montmorillonite and polyimide composite porous membrane comprises the following steps:
1) mixing the intercalation agent and montmorillonite in water, and heating at 60-120 ℃ for 4-48h, preferably at 80-100 ℃ for 24-36 h; washing and filtering the reacted mixed solution, and treating the filtered product in a vacuum oven at 60-120 ℃ to obtain organic montmorillonite;
wherein the intercalating agent is one or more of long-chain alkyl quaternary ammonium salts such as dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the intercalating agent to the montmorillonite is 0/1-3/1;
2) adding the modified organic montmorillonite and ethanol into a strong polar solvent, and performing ultrasonic treatment to uniformly disperse the organic montmorillonite and the ethanol, preferably performing ultrasonic treatment for 1-5 hours; then adding polyimide to completely dissolve the polyimide to obtain a casting solution; dropping the casting film on a release film, blade-coating to form a film, soaking the film in a coagulating bath to solidify the film to obtain a porous film, and carrying out heat treatment on the obtained porous film at 60-150 ℃ to obtain an organic montmorillonite/polyimide mixed film;
wherein the mass fraction of the polyimide in the film casting solution is 10-20%, the mass of the ethanol is 0.1-15% of the mass of the polyimide, and the mass of the modified organic montmorillonite is 0.1-15% of the mass of the polyimide; the strong polar solvent is any one or mixture of any several of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
The invention further provides the organic montmorillonite and polyimide composite porous membrane prepared by the preparation method.
The invention further provides the application of the organic montmorillonite and polyimide composite porous membrane in a lithium ion battery.
The invention has the beneficial effects that: the invention realizes the research of the electrochemical performance of the organic montmorillonite and polyimide composite porous membrane in a battery system, prepares the filler organic montmorillonite with a semi-organic structure by adopting a simple intercalation modification method, and realizes the physical blending of the organic montmorillonite and the polyimide by ultrasonic dispersion and heating stirring, thereby preparing the composite porous membrane with good compatibility and avoiding the reduction of the electrochemical performance caused by stronger interface effect between the filler and a polymer matrix membrane. In addition, the organic montmorillonite has a nano silicate structure, and can enhance the electrochemical properties such as ionic conductivity and the like of the lithium ion battery.
Drawings
FIG. 1 is an infrared spectrum of montmorillonite, organo montmorillonite and cetyltrimethylammonium bromide;
FIG. 2 is an X-ray diffraction spectrum of montmorillonite and organo montmorillonite;
FIG. 3 is a surface SEM image of a composite porous membrane of organic montmorillonite and polyimide;
FIG. 4 is a SEM image of the cross section of the composite porous membrane of organic montmorillonite and polyimide;
FIG. 5 is a mass impedance spectrum of a lithium ion battery assembled with a polyimide film, an organic montmorillonite and a polyimide composite porous film respectively;
FIG. 6 is an interface impedance spectrum of a lithium ion battery assembled with a polyimide film, an organic montmorillonite and a polyimide composite porous film respectively;
FIG. 7 is a diagram of the cycle performance test of a lithium ion battery assembled by a polyimide film, organic montmorillonite and a polyimide composite porous film respectively.
Detailed Description
To further illustrate the technical solution of the present invention, the following specific examples are given. It should be understood that the present invention has been shown and described only by way of illustration and description, and it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention or exceeding the scope of the claims.
The positive electrode material used in the following examples of the present invention was LiCoO2。
Example 1
1) Preparation of organic montmorillonite
3.0g of montmorillonite (MMT) was added to 120mL of deionized water, heated and stirred at 80 ℃ for 0.5h, then 1.5g of cetyltrimethylammonium bromide (CTAB) was added thereto, and reacted at 80 ℃ for 4 h. After the reaction is finished, the organic montmorillonite is placed for 24 hours, is filtered and cleaned, is dried for 12 hours at the temperature of 80 ℃, and is ground to obtain the modified organic montmorillonite (OMMT). FIG. 1 is an infrared spectrum of montmorillonite, organo montmorillonite and cetyl trimethyl ammonium bromide. FIG. 2 is the X-ray diffraction spectrum of montmorillonite and organic montmorillonite.
2) Preparation of organic montmorillonite and polyimide composite porous membrane
Dissolving polyimide in N, N-dimethylacetamide, heating and stirring for 4h in an oil bath at 60 ℃, then adding ethanol and the modified organic montmorillonite to prepare an organic montmorillonite and polyimide casting solution (the mass fraction of the polyimide in the casting solution is 17%, the mass of the ethanol is 10% and the mass of the modified organic montmorillonite is 7%) and dripping the organic montmorillonite and polyimide casting solution on a release film, blade-coating the solution into a film by using a scraper of 80 microns, soaking the film in a coagulating bath of ethanol/N, N-dimethylacetamide for 15min, and drying the obtained wet film at 120 ℃ for 12h to obtain the organic montmorillonite and polyimide composite porous film. The organic montmorillonite can be uniformly dispersed in the matrix membrane (plain SEM as shown in FIG. 3, cross-sectional SEM as shown in FIG. 4) to form composite porous membrane (OMMT/PI-7). The organic montmorillonite and the matrix membrane have good compatibility and are not easy to agglomerate.
The method for detecting the performance of the lithium ion battery with the prepared organic montmorillonite and polyimide composite porous membrane comprises the following steps:
(1) cutting the organic montmorillonite and polyimide composite porous membrane into a circle with the diameter of 19mm, and respectively assembling a positive electrode shell, a positive electrode, a membrane, a lithium sheet, an electrolyte, a negative electrode shell, a positive electrode shell, a stainless steel sheet, a membrane, a stainless steel sheet, an electrolyte, a negative electrode shell and the positive electrode shell, the lithium sheet, the membrane, the lithium sheet, the electrolyte and the negative electrode shell into a lithium ion battery in an argon glove box in sequence;
(2) testing the multiplying power and the cycle performance of the assembled positive shell-positive electrode-membrane-lithium plate-electrolyte-negative shell battery on a blue-electricity system; and testing the bulk impedance and the interfacial impedance of the organic montmorillonite on an electrochemical workstation by using the assembled positive electrode shell-stainless steel sheet-membrane-stainless steel sheet-electrolyte-negative electrode shell and the assembled positive electrode shell-lithium sheet-membrane-lithium sheet-electrolyte-negative electrode shell lithium ion battery.
Ion conductivity test of lithium ion battery assembled by organic montmorillonite and polyimide composite porous membrane
Assembling a lithium ion battery in an argon glove box, assembling according to the sequence of a positive electrode shell, a stainless steel sheet, a membrane, a stainless steel sheet, an electrolyte and a negative electrode shell, and testing the assembled battery on an electrochemical workstation by using an alternating current impedance method, wherein the frequency and the amplitude of the test are respectively 0.01Hz-10 Hz5Hz and 5 mV.
The results show that the bulk impedance of the polyimide film (OMMT/PI-0) assembled into a lithium ion battery is 1.49 Ω (see FIG. 5), and the ionic conductivity is 1.17 mS/cm. And the bulk impedance of the organic montmorillonite and polyimide composite porous membrane is 1.34 omega (as shown in figure 5), and the ionic conductivity is 1.41 mS/cm.
Interface impedance test of lithium ion battery assembled by organic montmorillonite and polyimide composite porous membrane
Assembling the lithium ion battery in an argon glove box, assembling according to the sequence of a positive electrode shell, a lithium sheet, a membrane, a lithium sheet, electrolyte and a negative electrode shell, and testing the assembled battery on an electrochemical workstation by using an alternating current impedance method, wherein the frequency and the amplitude of the test are respectively 0.01Hz-105Hz and 5 mV.
The results showed that the interface impedance of the polyimide film assembled lithium ion battery was 130 Ω. The interfacial impedance of the lithium ion battery assembled by the organic montmorillonite and the polyimide composite porous membrane is 93 omega (as shown in figure 6).
Cycle performance test of lithium ion battery assembled by organic montmorillonite and polyimide composite porous membrane
Assembling the lithium ion battery in an argon glove box, assembling according to the sequence of a positive electrode shell, a positive electrode, a membrane, a lithium sheet, electrolyte and a negative electrode shell, and testing the assembled battery in a blue test system, wherein the test voltage range is 2.4V-4.2V, and the current density is 0.2C.
The result shows that the lithium ion battery assembled by the polyimide film can stably circulate for 50 circles under 0.2 ℃, and the specific discharge capacity after 80 circles of circulation is 57.9 mAh/g. The lithium ion battery assembled by the organic montmorillonite and polyimide composite porous membrane can stably circulate for 80 circles at 0.2 ℃, and the specific discharge capacity after 80 circles of circulation is 119.8mAh/g (as shown in figure 7).
Example 2
The preparation steps of the organic montmorillonite are the same as the above.
Polyimide is dissolved in N, N-dimethylacetamide, heated and stirred for 4 hours in an oil bath at the temperature of 60 ℃, and then ethanol and the modified organic montmorillonite are added to prepare organic montmorillonite and polyimide casting solution (the mass fraction of the polyimide in the casting solution is 17%, the mass of the ethanol is 10% and the mass of the modified organic montmorillonite is 3%). The film formation process is the same as above (the porous membrane is OMMT/PI-3).
After the lithium ion battery was assembled in the same manner as in example 1, the results of the ionic conductivity test and the interfacial impedance test showed that the ionic conductivity of the lithium ion battery assembled with the composite porous membrane of organic montmorillonite and polyimide was 1.30mS/cm, the interfacial impedance was 122 Ω (as shown in fig. 6), and the specific discharge capacity after 80 cycles at 0.2C was 62.9mAh/g (as shown in fig. 7).
Example 3
The preparation steps of the organic montmorillonite are the same as above.
Polyimide is dissolved in N, N-dimethylacetamide, heated and stirred for 4 hours in an oil bath at 60 ℃, and then ethanol and the modified organic montmorillonite are added to prepare organic montmorillonite and polyimide casting solution (the mass fraction of the polyimide in the casting solution is 17%, the mass of the ethanol is 10% and the mass of the modified organic montmorillonite is 5%). The film formation process is the same as above (the porous membrane is OMMT/PI-5).
After the lithium ion battery was assembled in the same manner as in example 1, the results of the ionic conductivity test and the interfacial impedance test showed that the ionic conductivity of the lithium ion battery assembled with the composite porous membrane of organic montmorillonite and polyimide was 1.37mS/cm, the interfacial impedance was 108 Ω (as shown in fig. 6), and the specific discharge capacity after 80 cycles at 0.2C was 69.7mAh/g (as shown in fig. 7).
Example 4
Polyimide is dissolved in N, N-dimethylacetamide, heated and stirred for 4 hours in an oil bath at 60 ℃, and then ethanol and the modified organic montmorillonite are added to prepare organic montmorillonite and polyimide casting solution (the mass fraction of the polyimide in the casting solution is 17%, the mass of the ethanol is 10% and the mass of the modified organic montmorillonite is 10%). The film formation process is the same as above (the porous membrane is OMMT/PI-10).
After the lithium ion battery is assembled by the same method as that of the example 1, the ionic conductivity test and the interface impedance test result show that the ionic conductivity of the lithium ion battery assembled by the organic montmorillonite and the polyimide composite porous membrane is 0.99mS/cm, the interface impedance is 98 omega (shown in figure 6), and the specific discharge capacity after 80 cycles at 0.2 ℃ is 119.1mAh/g (shown in figure 7).
Through the exploration of the electrochemical performance of the lithium ion battery assembled by the organic montmorillonite and polyimide composite porous membrane, compared with the electrochemical performance of the lithium ion battery assembled by the polyimide membrane, the ionic conductivity and the cycle performance are both greatly improved, and the interface impedance is effectively reduced. The nanometer silicate of the organic montmorillonite and the carbonate solvent in the electrolyte have good affinity, and the steric hindrance effect caused by the added organic montmorillonite can reduce the interaction among polymer molecular chains and hinder the crystallization of the polymer chains, thereby being beneficial to increasing the amorphous region of the polymer, promoting the ion transmission and further improving the ion conductivity and other electrochemical properties.
The following experiments and applications can be fully proved: the electrochemical performance of the lithium ion battery can be effectively improved by compounding the organic montmorillonite and the polyimide.
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The invention is not the best known technology.
Claims (6)
1. A preparation method of organic montmorillonite and polyimide composite porous membrane is characterized by comprising the following steps:
1) mixing an intercalating agent and an aqueous solution of montmorillonite, heating at 60-120 ℃ for 4-48h, washing and filtering the reacted mixed solution, and treating the filtered product in a vacuum oven at 60-120 ℃ to obtain modified organic montmorillonite;
the intercalation agent is one or more of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide long-chain alkyl quaternary ammonium salt, and the mass ratio of the intercalation agent to the montmorillonite is 0/1-3/1;
2) adding the modified organic montmorillonite and ethanol into a strong polar solvent, and uniformly dispersing the organic montmorillonite and the ethanol through ultrasonic treatment; then adding polyimide to completely dissolve the polyimide to obtain a membrane casting solution; dropping the casting film on a release film, blade-coating to form a film, soaking the film in a coagulating bath to solidify the film to obtain a porous film, and carrying out heat treatment on the obtained porous film at 60-150 ℃ to obtain an organic montmorillonite/polyimide mixed film;
wherein the mass fraction of the polyimide in the film casting solution is 10-20%, the mass of the ethanol is 0.1-15% of the mass of the polyimide, and the mass of the modified organic montmorillonite is 0.1-15% of the mass of the polyimide; the strong polar solvent is any one or mixture of any several of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
2. The method for preparing the organic montmorillonite and polyimide composite porous membrane according to claim 1, wherein in the step (1), the intercalating agent and the montmorillonite are mixed in the water solution and heated at 80-100 ℃ for 24-36 h.
3. The method for preparing organic montmorillonite and polyimide porous membrane according to claim 1, wherein the treatment time of the ultrasonic treatment in step (2) is 1-5 h.
4. The method for preparing the organic montmorillonite and polyimide porous membrane according to claim 1, wherein the organic montmorillonite and polyimide composite porous membrane in the step (2) is subjected to heat treatment at 80-120 ℃ in a vacuum oven.
5. The organic montmorillonite and polyimide composite porous membrane prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the composite porous membrane of organic montmorillonite and polyimide according to claim 5 in a lithium ion battery.
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