CN112062989A - Polyimide aerogel lithium battery diaphragm and preparation method thereof - Google Patents
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Abstract
The invention provides a polyimide aerogel lithium battery diaphragm and a preparation method thereof, wherein 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 polyamide acid solution; adding a poor organic solvent into the polyamic acid solution to obtain a uniformly mixed solution system on the premise of ensuring that the polyamic acid is not precipitated; adding a polyamino crosslinking agent into the uniformly mixed solution system, uniformly mixing, adding an imidization reagent, uniformly mixing again, and removing bubbles in vacuum to obtain a coating solution; coating the film coating liquid on a substrate, standing, and aging after the film coating liquid is gelled to obtain a polyimide wet gel film; and (3) carrying out solvent replacement on the polyimide wet gel film, and carrying out supercritical drying to obtain the polyimide aerogel lithium battery diaphragm. The diaphragm has average pore diameter of more than hundreds of nanometers, high porosity, high wettability and high temperature resistance.
Description
Technical Field
The invention relates to a polyimide aerogel lithium battery diaphragm and a preparation method thereof, and belongs to the technical field of lithium battery diaphragms.
Background
In recent years, due to the problems of energy shortage and environmental pollution, the replacement of conventional fuel-oil vehicles with clean and pollution-free electric vehicles has become a necessary trend. The lithium battery has become the main choice of the power battery due to the advantages of large specific capacity, long cycle life, no memory effect, quick charging and the like. The diaphragm is a key component of the lithium battery, has the main functions of blocking the physical contact of the anode and the cathode of the battery and allowing electrolyte ions to freely pass through, and is an important determinant factor of the capacity, the circulation capacity and the safety of the battery.
The traditional lithium battery diaphragm is mainly a polyolefin diaphragm, and can be fused when the temperature of the battery exceeds 160 ℃, so that the positive electrode and the negative electrode are in contact and short circuit is caused, the battery is ignited and even explodes, and the life safety of a user is greatly threatened; and the polyolefin diaphragm also has the problems of low porosity and poor electrolyte wettability, and can not meet the use requirements of high-capacity and high-rate lithium batteries.
Polyimide (PI) is a high-molecular insulating material with excellent comprehensive performance, has excellent dielectric property, thermal stability, mechanical property and chemical stability, can be used for a long time at the temperature of more than 300 ℃, can be used for preparing a battery diaphragm, can greatly reduce the risk of safety accidents caused by overheating in a battery, and is an ideal battery diaphragm material. The existing method for preparing the polyimide battery diaphragm mainly comprises an electrostatic spinning method, a phase inversion method and an inorganic filler removal method. The polyimide nanofiber membrane prepared by the electrostatic spinning method is good in heat resistance, but the charge retention rate of a lithium battery is low due to the fact that the pore diameter of the polyimide nanofiber membrane is too large, and the short circuit phenomenon is often caused. The phase inversion method and the inorganic filler removal method are used for preparing the polyimide diaphragm, and a pore-forming agent is needed, so that the pore-forming agent is difficult to remove completely, the pore diameter of the polyimide diaphragm is not uniformly distributed, the porosity is low (about 50 percent), and the charge-discharge efficiency of the lithium battery is influenced. How to prepare the polyimide battery diaphragm with uniform pore size distribution, high porosity and high wettability is a technical problem.
The polyimide aerogel prepared by utilizing the sol-gel and supercritical drying technology can prepare a diaphragm material with porosity of more than 80%, uniform pore size distribution and high wettability, but because the pore sizes of the polyimide aerogel are all nano-scale (10-40 nm), the efficiency of electrolyte ions passing through the diaphragm is low, the average pore size of the polyimide aerogel is improved to be more than hundreds of nanometers, the efficiency of the electrolyte ions passing through the diaphragm is improved, and the technical difficulty of judging whether the polyimide aerogel can become an ideal diaphragm material of a lithium battery is achieved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polyimide aerogel lithium battery diaphragm with an average pore diameter of more than hundreds of nanometers, high porosity, high wettability and high temperature resistance and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a polyimide aerogel lithium battery diaphragm comprises the following steps:
in the first step, a polyamic acid solution is prepared,
a1.1, 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;
a1.2, adding a poor organic solvent into the polyamic acid solution prepared in the step A1.1, and uniformly mixing the solution system on the premise of ensuring that the polyamic acid is not precipitated;
secondly, preparing a polyimide wet gel film;
a2.1, adding a polyamino crosslinking agent into the solution system prepared in the step A1.2, uniformly mixing, then adding an imidization reagent, uniformly mixing, and then carrying out vacuum defoaming to obtain a coating solution;
a2.2, coating the coating liquid prepared in the step A2.1 on a substrate, standing, and obtaining a polyimide wet gel film after the coating liquid is gelled and aged;
and thirdly, performing solvent replacement and supercritical drying on the polyimide wet gel film prepared in the second step to obtain the polyimide aerogel lithium battery diaphragm.
Further, the aromatic dianhydride is one of pyromellitic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride and 3,3',4,4' -benzophenone tetracarboxylic dianhydride; the aromatic diamine is one of p-phenylenediamine, 2' -dimethyl-4, 4' -Diaminobiphenyl (DMBZ), 2- (4-aminophenyl) -5-aminobenzimidazole and 4,4' -diaminodiphenyl ether.
Further, the solid content (mass percentage of the aromatic dianhydride monomer and the aromatic diamine monomer in the reaction solution before the condensation polymerization reaction) of the mixed reaction solution in the step A1.1 is 5-15%. The solid content is too high, the viscosity of a reaction system is too high, uniform reaction among monomers is difficult, and a large amount of low polymers which are difficult to gel exist in the reaction system, so that the density of the final aerogel diaphragm is difficult to accurately regulate and control. If the solid content of the reaction solution is too low, the wet gel strength of the obtained polyamic acid solution in the subsequent gelation reaction process is poor, and the prepared diaphragm material has poor mechanical properties and is easy to break.
Further, the solid content of the reaction solution in the step a1.1 is preferably 7% to 10%, within this range, the prepared polyamic acid solution has a high molecular weight, and the prepared polyimide aerogel diaphragm has good mechanical properties.
Further, the polyamic acid solution of high molecular weight means a polymerization degree of not less than 33. If the polymerization degree is too low, the molecular weight of the polyamic acid solution is too small, the wet gel strength is poor in the subsequent gelation reaction process, and the prepared diaphragm material is poor in mechanical property and easy to break.
Furthermore, the molar ratio of the aromatic dianhydride to the aromatic diamine is 1 (0.97-0.99).
Further, in the condensation polymerization reaction step, the time is 8-72 hours, and the temperature is 0-40 ℃.
Further, the organic solvent is one or a mixture of two of N-methyl pyrrolidone, N-dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide in any proportion.
Further, the adding amount of the poor organic solvent in the step A1.2 is 10 to 30 percent of the organic solvent in the step A1.1 by mass. Too much addition of the poor solvent causes severe phase separation of the polyamic acid in the solution to precipitate, and polyimide wet gel cannot be prepared; the poor solvent is added in a small amount, so that the polyamic acid is slightly phase-separated in the solution, and macropores formed in polyimide wet gel after imidization are less, so that the electrolyte ion passing efficiency of the polyimide aerogel diaphragm is low.
Further, the kind of the poor organic solvent in the step a1.2 is different from that in the step a1.1, and the poor organic solvent is one or a mixture of more of methanol, ethanol, propanol, glycerol, acetone, acetic acid and ethyl acetate in any proportion.
Further, the adding amount of the polyamino crosslinking agent in the step A2.1 is 3 to 5 percent of the total mass of the aromatic dianhydride and the aromatic diamine in the step A1.1 by mass.
Further, the polyamino crosslinking agent in step a1.1 is preferably one of 1,3, 5-triaminobenzene, 1,3, 5-tris (aminophenoxy) benzene, 2, 6-bis (4' -aminophenyl) -4- (4' -aminophenyl) pyridine (TAPP), 3' -diaminobenzidine, and octaaminophenyl POSS.
Further, the imidization reagent comprises a catalyst and a dehydrating agent, and the proportion of the catalyst and the dehydrating agent is the conventional proportion; the imidizing agent is a known technique in the art, and includes a catalyst such as pyridine, picoline, triethylamine and the like, a dehydrating agent such as acetic anhydride, acetyl chloride, thionyl chloride, a phosphorus halide, an organic silicon compound, dicyclohexylcarbodiimide and the like.
Further, the coating solution of the step A2.2 is coated by a scraper, and a scraping gap between the scraper and the base material is controlled to be 50-300 μm.
And further, aging the polyimide wet gel for 24 hours at room temperature, and aging the polyimide wet gel to promote the wet gel to have complete imidization reaction. The ageing temperature and time depend on the reactivity of the monomers, and gel ageing is a technique known in the art and chosen by the person skilled in the art according to the actual requirements.
Further, solvent substitution and supercritical drying are well known in the art, and the solvent may be commonly used ethanol, acetone or the like, and those skilled in the art may select the solvent and the process according to the particular circumstances.
A polyimide aerogel lithium battery diaphragm is prepared by the method.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method of the polyimide aerogel lithium battery diaphragm, poor solvents are used for inducing the micro-phase separation of the polyamic acid in the solution, and a large number of macropores which are uniformly distributed and have hundreds of nanometers are formed after polyimide wet gel is formed through imidization, so that the problems that the polyimide aerogel is small in pore diameter as a battery diaphragm material and the efficiency of electrolyte ions passing through the diaphragm is low are solved; the polyimide aerogel diaphragm with controllable porosity and pore size can be prepared by adjusting the solid content and the addition of the poor solvent.
(2) The polyimide aerogel diaphragm prepared by the invention has the glass transition temperature of more than 300 ℃, can still keep good dimensional stability at 300 ℃, and can well improve the safety performance of the battery.
(3) The polyimide aerogel diaphragm prepared by the method has the porosity of over 80 percent, has excellent electrolyte wettability and liquid absorption performance, and can effectively solve the problem of poor electrolyte wettability of the traditional diaphragm material.
Drawings
Fig. 1 is a flow chart of a preparation process of a polyimide aerogel lithium battery separator according to the present invention.
Detailed Description
In order to make the technical solution of the present invention more comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
In this embodiment, the preparation method provided by the invention is used for preparing the polyimide aerogel lithium battery diaphragm, and the steps are as follows:
1. 8.83g (30mmol) of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 6.18g (29.1mmol) of 2,2 '-dimethyl-4, 4' -diaminobiphenyl were dissolved in 285.19g of NMP, and condensation polymerization was carried out at 25 ℃ for 24 hours to obtain a polyamic acid solution; 28.52g of ethanol was added to the polyamic acid solution to uniformly mix the solution system.
2. Adding 0.45g of cross-linking agent 1,3, 5-tri (aminophenoxy) benzene into a polyamic acid solution system, stirring for 5min at 25 ℃, adding an imidization reagent (24mL of acetic anhydride and 19mL of pyridine), uniformly mixing, and removing bubbles in vacuum to obtain a coating solution; coating the film coating liquid on a substrate by a scraper, controlling the scraping gap between the scraper and the substrate to be 100 mu m to form a polyamic acid film, standing, aging at room temperature for 24h to obtain the polyimide wet gel film after the film coating liquid gels to form the polyimide wet gel film.
3. Subjecting the obtained polyimide wet gel film to solvent replacement, repeatedly soaking with ethanol for 3 times, and subjecting to supercritical CO2The mixture is dried and then is dried,and drying for 8h at the temperature of 60 ℃ under the pressure of 15MPa to obtain the polyimide aerogel lithium battery diaphragm.
The data of the test results of the polyimide aerogel lithium battery separator obtained in this example are shown in table 1.
Example 2
The preparation conditions and procedure of the polyimide aerogel lithium battery separator were the same as in example 1 except that 6.24g (29.4mmol) of 2,2 '-dimethyl-4, 4' -diaminobiphenyl, 135.66g of NMP, 27.13g of methanol as a poor solvent, 0.60g of 1,3, 5-tris (aminophenoxy) benzene as a crosslinking agent were added, and a condensation polymerization reaction was carried out at 40 ℃ for 8 hours while controlling the blade gap between the doctor blade and the base material to be 300. mu.m, and the data of the performance test results of the polyimide aerogel lithium battery separator are shown in Table 1.
Example 3
The preparation conditions and procedure of the polyimide aerogel lithium battery separator were the same as those of example 1 except that 6.31g (29.7mmol) of 2,2 '-dimethyl-4, 4' -diaminobiphenyl, 85.78g of NMP, 25.73g of acetic acid as a poor solvent, 0.76g of 1,3, 5-tris (aminophenoxy) benzene as a crosslinking agent were added, and condensation polymerization was carried out at 0 ℃ for 72 hours while controlling the blade gap between the doctor blade and the base material to be 50 μm, and the data of the performance test results of the polyimide aerogel lithium battery separator are shown in Table 1.
Example 4
The preparation conditions and procedure of the polyimide aerogel lithium battery separator were the same as in example 1 except that 27g of ethyl acetate was used as a poor solvent, and the data of the performance test results of the polyimide aerogel lithium battery separator are shown in table 1.
Example 5
The preparation conditions and process of the polyimide aerogel lithium battery separator were the same as in example 1 except that 27g of acetone was used as a poor solvent, and the data of the performance test results of the polyimide aerogel lithium battery separator are shown in table 1.
Comparative example 1
1. 8.83g (30mmol) of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 6.18g (29.1mmol) of 2,2 '-dimethyl-4, 4' -diaminobiphenyl were dissolved in 135.1g of NMP, and condensation polymerization was carried out at 25 ℃ for 24 hours to obtain a polyamic acid solution.
2. Adding 0.46g of cross-linking agent 1,3, 5-tri (aminophenoxy) benzene into a polyamic acid solution system, stirring for 5min at 25 ℃, adding an imidizing reagent (24mL of acetic anhydride and 19mL of pyridine), uniformly mixing, and removing bubbles in vacuum to obtain a coating solution; coating the coating solution on a substrate by a scraper to form a polyamic acid film (100 mu m), standing, forming a polyimide wet gel film by the gel of the coating solution, and aging at room temperature for 24h to obtain the polyimide wet gel film.
3. Subjecting the obtained polyimide wet gel film to solvent replacement, repeatedly soaking with ethanol for 3 times, and subjecting to supercritical CO2Drying the lithium battery separator at 60 ℃ under 15MPa for 8h to obtain the polyimide aerogel lithium battery separator, wherein the test result data are listed in Table 1.
Table 1 performance test results of polyimide aerogel battery separators obtained in examples 1 to 5 and comparative example 1
As can be seen from the data in Table 1, compared with comparative example 1, the polyimide aerogel lithium battery diaphragm provided by the application has a larger average pore size, so that lithium ions can pass through the diaphragm more easily, the conductivity is obviously improved, the better mechanical property of the polyimide aerogel lithium battery diaphragm is kept, and the polyimide aerogel lithium battery diaphragm is ideal in heat resistance and electrolyte wettability.
The above embodiments are only intended to illustrate the technical solution of the present invention, but not to limit it, and a person skilled in the art can modify the technical solution of the present invention or substitute it with an equivalent, and the protection scope of the present invention is subject to the claims.
Claims (10)
1. The preparation method of the polyimide aerogel lithium battery diaphragm is characterized by comprising the following 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 poor organic solvent into the polyamic acid solution to obtain a uniformly mixed solution system on the premise of ensuring that the polyamic acid is not precipitated;
adding a polyamino crosslinking agent into the uniformly mixed solution system, uniformly mixing, adding an imidization reagent, uniformly mixing again, and removing bubbles in vacuum to obtain a coating solution;
coating the film coating liquid on a substrate, standing, and aging after the film coating liquid is gelled to obtain a polyimide wet gel film; and (3) carrying out solvent replacement on the polyimide wet gel film, and carrying out supercritical drying to obtain the polyimide aerogel lithium battery diaphragm.
2. The method according to claim 1, wherein the aromatic dianhydride is one of pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride, and 3,3',4,4' -benzophenonetetracarboxylic dianhydride; the aromatic diamine is one of p-phenylenediamine, 2' -dimethyl-4, 4' -diaminobiphenyl, 2- (4-aminophenyl) -5-aminobenzimidazole and 4,4' -diaminodiphenyl ether; the organic solvent is one or two of N-methyl pyrrolidone, N-dimethyl acetamide, N-dimethyl formamide and dimethyl sulfoxide.
3. The method according to claim 1 or 2, wherein the molar ratio of the aromatic dianhydride monomer to the aromatic diamine monomer is 1 (0.97 to 0.99), and the mass percentage of the aromatic dianhydride monomer to the aromatic diamine monomer added with the organic solvent is 5 to 15 percent.
4. The method of claim 1, wherein the condensation polymerization reaction is carried out for a time of 8 to 72 hours at a temperature of 0 to 40 ℃.
5. The method according to claim 1, wherein the poor organic solvent is added in an amount of 10 to 30% by mass based on the mass of the organic solvent.
6. The method of claim 1, wherein the poor organic solvent is one or more of methanol, ethanol, propanol, glycerol, acetone, acetic acid, and ethyl acetate.
7. The method according to claim 1, wherein the polyamino crosslinking agent is added in an amount of 3 to 5% by mass based on the total mass of the aromatic dianhydride and the aromatic diamine; the polyamino cross-linking agent is selected from one of 1,3, 5-triaminobenzene, 1,3, 5-tri (aminophenoxy) benzene, 2, 6-bis (4' -aminophenyl) -4- (4' -aminophenyl) pyridine (TAPP), 3' -diaminobenzidine and octaaminophenyl POSS.
8. The method of claim 1, wherein the imidizing agent comprises a catalyst comprising pyridine, picoline, triethylamine, and a dehydrating agent comprising acetic anhydride, acetyl chloride, thionyl chloride, phosphorus halides, organosilicon compounds, dicyclohexylcarbodiimide.
9. The method according to claim 1, wherein the coating solution is applied to the substrate by a doctor blade, and a blade gap between the doctor blade and the substrate is controlled to be 50 to 300 μm.
10. A polyimide aerogel lithium battery separator prepared by the method of claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112940307A (en) * | 2020-12-31 | 2021-06-11 | 中国科学技术大学 | Polyimide aerogel film and preparation method and application thereof |
| CN113462012A (en) * | 2021-07-19 | 2021-10-01 | 中国科学技术大学 | Flexible linear high-temperature-resistant polyimide aerogel battery diaphragm, preparation method thereof and lithium ion battery |
| CN114976472A (en) * | 2022-05-17 | 2022-08-30 | 刘文洁 | Aerogel battery diaphragm and preparation method thereof |
| CN115693021A (en) * | 2022-11-14 | 2023-02-03 | 江南大学 | Polyimide fiber/aerogel composite membrane and preparation method thereof |
| WO2023074909A1 (en) * | 2021-11-01 | 2023-05-04 | 株式会社スリーダムアライアンス | Polyimide porous film, electrode structure, and power storage device |
| CN118047947A (en) * | 2024-01-23 | 2024-05-17 | 江南大学 | Metal coordination polyimide aerogel composite diaphragm and preparation method and application thereof |
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| CN112940307A (en) * | 2020-12-31 | 2021-06-11 | 中国科学技术大学 | Polyimide aerogel film and preparation method and application thereof |
| CN112940307B (en) * | 2020-12-31 | 2023-10-20 | 中国科学技术大学 | Polyimide aerogel film and preparation method and application thereof |
| CN113462012A (en) * | 2021-07-19 | 2021-10-01 | 中国科学技术大学 | Flexible linear high-temperature-resistant polyimide aerogel battery diaphragm, preparation method thereof and lithium ion battery |
| WO2023074909A1 (en) * | 2021-11-01 | 2023-05-04 | 株式会社スリーダムアライアンス | Polyimide porous film, electrode structure, and power storage device |
| CN114976472A (en) * | 2022-05-17 | 2022-08-30 | 刘文洁 | Aerogel battery diaphragm and preparation method thereof |
| CN115693021A (en) * | 2022-11-14 | 2023-02-03 | 江南大学 | Polyimide fiber/aerogel composite membrane and preparation method thereof |
| CN118047947A (en) * | 2024-01-23 | 2024-05-17 | 江南大学 | Metal coordination polyimide aerogel composite diaphragm and preparation method and application thereof |
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