CN113851730A - High-temperature-resistant polymer electrolyte membrane and preparation method thereof - Google Patents
High-temperature-resistant polymer electrolyte membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-temperature-resistant polymer electrolyte membrane, which comprises the following steps: s1, dissolving the first polymer in an organic solvent to obtain a first mixed solution; s2, adding lithium salt into the first mixed solution to obtain a second mixed solution; s3, adding aromatic diacid chloride into the second mixed solution, adding aromatic diamine after dissolving, and stirring to react completely to obtain polymer electrolyte slurry; s4, coating the polymer electrolyte slurry on a substrate to obtain a wet film; s5, drying to obtain a finished product; the addition amount of the first polymer: the addition amount of aromatic diacid chloride: the addition amount of the aromatic diamine is (1-3): (2 to 3) and (1 to 2). Correspondingly, the invention also provides the high-temperature-resistant polymer electrolyte membrane prepared by the method, which has the advantages of good mechanical strength, stable structure, high heat resistance and excellent film forming property.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a high-temperature-resistant polymer electrolyte membrane and a preparation method thereof.
Background
In order to meet the increasing demand for lithium batteries for consumer electronics and electric vehicles, all-solid-state lithium batteries have attracted considerable attention in recent years due to their superior safety and ultra-high energy density. Conventional lithium batteries containing organic liquid electrolytes exhibit serious safety problems of toxicity, flammability, corrosiveness and poor chemical stability, which can be fundamentally alleviated by using solid electrolytes as an alternative. The all-solid-state lithium battery is divided into three types according to different types of solid electrolytes: polymers, oxides and sulfides. The polymer all-solid-state battery is the most similar to the existing liquid battery production process, and is the most industrialized all-solid-state lithium battery. However, the polymer electrolyte membrane has limited development and application due to low ionic conductivity, poor mechanical strength and heat resistance, and the like.
The polymer electrolyte is mainly prepared by dissolving polymer (PEO, PVDF, PVDF-HFP, PPC, PMMA, etc.) in solvent (NMP, DMAC, DMF, acetonitrile), and adding lithium salt (LiPF)6，LiCLO4LiTFSI, etc.), a plasticizer or an ionic liquid, and an inorganic oxide, etc. to prepare an electrolyte slurry. And forming the electrolyte slurry into a film by a solution casting method or a blade coating method, and then drying at high temperature to volatilize the solvent to prepare the polymer electrolyte film. Because the existing polymer solid electrolytes such as PEO, PVDF, PPC, PMMA and the like have lower melting points and poorer structural stability, potential safety hazards are easy to appear. Therefore, it is often required to improve the structural stability of the polymer electrolyte by adding an inorganic oxide or compounding various structural supports. However, the improved polymer electrolyte has general mechanical strength and heat resistance, and general film forming quality, and when the battery is out of control due to heat, the electrolyte film is easy to deform in structure, so that the contact of the positive electrode and the negative electrode is short-circuited, and safety accidents are caused. Although the heat resistance of the polymer electrolyte membrane can be improved by adding an inorganic oxide or compounding various porous membrane supports, the ionic conductivity of the polymer electrolyte membrane is severely reduced due to uneven dispersion of the oxide and the composite support, and the battery capacity and the cycle performance are severely damaged.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a high-temperature-resistant polymer electrolyte membrane, wherein aromatic diacid chloride and aromatic diamine are added into a polymer electrolyte, aromatic polyamide is synthesized in an in-situ polymerization mode, and a polymer electrolyte membrane with a uniform three-dimensional network structure is obtained by interpenetrating aromatic polyamide molecular chains and first polymer molecular chains.
The technical problem to be solved by the invention is to provide a high-temperature-resistant polymer electrolyte membrane which has good mechanical strength, stable structure, high heat resistance and excellent membrane forming performance.
In order to solve the technical problem, the invention provides a preparation method of a high-temperature-resistant polymer electrolyte membrane, which comprises the following steps:
s1, dissolving the first polymer in an organic solvent to obtain a first mixed solution;
s2, adding lithium salt into the first mixed solution to obtain a second mixed solution;
s3, adding aromatic diacid chloride into the second mixed solution, adding aromatic diamine after the aromatic diacid chloride is dissolved, and stirring and reacting completely to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the wet membrane of the polymer electrolyte to obtain a finished product;
the addition amount of the first polymer: the addition amount of aromatic diacid chloride: the addition amount of the aromatic diamine is (1-3): (2 to 3) and (1 to 2).
Preferably, the aromatic diacid chloride is terephthaloyl chloride and/or isophthaloyl chloride; the aromatic diamine is p-phenylenediamine and/or m-phenylenediamine.
Preferably, the first polymer comprises one or a combination of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polypropylene carbonate, and polymethyl methacrylate:
the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide and lithium difluorooxalato borate;
the organic solvent comprises one or more of N-methyl pyrrolidone, N-dimethyl acetamide, N-dimethyl formamide, acetonitrile and hexamethyl phosphoric triamide.
Preferably, in step S1, the first mixed solution includes 1 to 15% of the first polymer and 85 to 99% of the organic solvent.
Preferably, in step S1, calcium chloride or lithium chloride is also added to the organic solvent; the addition amount of the calcium chloride or the lithium chloride is 3-9% of the mass of the organic solvent.
Preferably, in step S2, the amount of the lithium salt added is 0.5 to 5% by mass of the first mixed solution.
Preferably, in step S3, the amount of the aromatic diamine added is 40% to 60% of the amount of the aromatic diacid chloride added.
Preferably, in step S3, during the reaction: the reaction temperature is-15 to 0 ℃, and the reaction time is 1 to 6 hours.
Preferably, in step S5, the drying temperature is 50-90 ℃ and the drying time is 4-8 h.
The invention also provides the high-temperature-resistant polymer electrolyte membrane prepared by the preparation method.
The implementation of the invention has the following beneficial effects:
1. according to the preparation method of the high-temperature-resistant polymer electrolyte membrane, the aromatic diacid chloride and the aromatic diamine are added into the polymer electrolyte, the aromatic diacid chloride and the aromatic diamine synthesize the aromatic polyamide in an in-situ polymerization mode, and the aromatic polyamide molecular chain and the first polymer molecular chain are mutually interpenetrated to form a three-dimensional network structure. The polymer electrolyte membrane with the molecular chain interpenetrating structure increases the interaction force between two molecular chains on one hand, and can improve the mechanical strength, the structural stability and the high temperature resistance of the polymer electrolyte membrane. On the other hand, the interpenetrating structure further reduces the crystallinity of the polymer and improves the ionic conductivity of the polymer electrolyte membrane.
2. Compared with simple physical mixing, the preparation method can obtain the polymer electrolyte membrane with more uniform mixed structure, and in the simple physical mixing process, the interpenetrating proportion of molecular chains is less, so that the electrolyte membrane has non-uniform structure, and finally the defects of insufficient local strength and heat resistance and the like are generated. According to the invention, by controlling the in-situ polymerization process, the two polymers can be fully mixed to the maximum extent, the molecular chain interpenetrating of a three-dimensional structure is realized, the polymer electrolyte membrane with uniform structure at each part is obtained, and the mechanical strength and the ionic conductivity are improved.
3. The polymer electrolyte membrane obtained by the invention has excellent processing and film-forming properties, and has certain flexibility while keeping certain rigidity. The rigid aromatic polyamide molecular chain and the soft polymer molecular chain form an interpenetrating network structure, so that the characteristics of high heat resistance, structural stability and the like of the aromatic polyamide are reserved, and the high ion transmission capability of the polymer is achieved.
Drawings
FIG. 1 is a graph showing a comparison of test performances of polymer electrolyte membranes obtained in examples 1 to 7 of the present invention and comparative examples 1 to 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below.
The existing polymer solid electrolyte has low melting point and poor structural stability, is easy to have potential safety hazard, and often needs to improve the structural stability of the polymer electrolyte by adding inorganic oxides or compounding various structural supports. However, the improved polymer electrolyte has general mechanical strength and heat resistance, and general film forming quality, and when the battery is out of control due to heat, the electrolyte film is easy to deform in structure, so that the contact of the positive electrode and the negative electrode is short-circuited, and safety accidents are caused. Although the heat resistance of the polymer electrolyte membrane can be improved by adding an inorganic oxide or compounding various porous membrane supports, the ionic conductivity of the polymer electrolyte membrane is severely reduced due to uneven dispersion of the oxide and the composite support, and the battery capacity and the cycle performance are severely damaged.
Therefore, the present invention provides a method for preparing a high temperature resistant polymer electrolyte membrane, comprising the steps of:
s1, dissolving the first polymer in an organic solvent to obtain a first mixed solution;
s2, adding lithium salt into the first mixed solution to obtain a second mixed solution;
s3, adding aromatic diacid chloride into the second mixed solution, adding aromatic diamine after the aromatic diacid chloride is dissolved, and stirring and reacting completely to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the wet membrane of the polymer electrolyte to obtain a finished product;
the addition amount of the first polymer: the addition amount of aromatic diacid chloride: the addition amount of the aromatic diamine is (1-3): (2-3) and (1-2);
according to the preparation method of the high-temperature-resistant polymer electrolyte membrane, the aromatic diacid chloride and the aromatic diamine are added into the polymer electrolyte, the aromatic diacid chloride and the aromatic diamine synthesize the aromatic polyamide in an in-situ polymerization mode, and the aromatic polyamide molecular chain and the first polymer molecular chain are mutually interpenetrated to form a three-dimensional network structure. The polymer electrolyte membrane with the molecular chain interpenetrating structure increases the interaction force between two molecular chains on one hand, and can improve the mechanical strength, the structural stability and the high temperature resistance of the polymer electrolyte membrane. On the other hand, the interpenetrating structure further reduces the crystallinity of the polymer and improves the ionic conductivity of the polymer electrolyte membrane.
Compared with simple physical mixing, the preparation method can obtain the polymer electrolyte membrane with more uniform mixed structure, and in the simple physical mixing process, the interpenetrating proportion of molecular chains is less, so that the electrolyte membrane has non-uniform structure, and finally the defects of insufficient local strength and heat resistance and the like are generated. According to the invention, by controlling the in-situ polymerization process, the two polymers can be fully mixed to the maximum extent, the molecular chain interpenetrating of a three-dimensional structure is realized, the polymer electrolyte membrane with uniform structure at each part is obtained, and the mechanical strength and the ionic conductivity are improved.
The polymer electrolyte membrane obtained by the invention has excellent processing and film-forming properties, and has certain flexibility while keeping certain rigidity. The rigid aromatic polyamide molecular chain and the soft polymer molecular chain form an interpenetrating network structure, so that the characteristics of high heat resistance, structural stability and the like of the aromatic polyamide are reserved, and the high ion transmission capability of the polymer is achieved.
Further, the addition amounts of the first polymer, the aromatic diacid chloride and the aromatic diamine affect the structural properties of the finally obtained polymer electrolyte membrane. The adding amount of the aromatic diacid chloride and the aromatic diamine influences the molecular weight of the generated aromatic polyamide, and meanwhile, the adding amount of the first polymer influences the uniformity of a three-dimensional network structure formed by the mutual interpenetration of the aromatic polyamide molecular chain and the first polymer molecular chain. Preferably, the first polymer is added in an amount of: the addition amount of aromatic diacid chloride: the adding amount of the aromatic diamine is (1-3): (2-3) and (1-2), preferably, the amount of the first polymer added is: the addition amount of aromatic diacid chloride: the amount of the aromatic diamine added is (1-2): (2-3) and (1-2), so that the obtained polymer electrolyte membrane has a more uniform and stable three-dimensional structure, higher mechanical strength, better high-temperature resistance and higher ionic conductivity.
Next, each step of the preparation method will be described in detail as follows.
In step S1, preferably, the first polymer includes one or a combination of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polypropylene carbonate (PPC), and polymethyl methacrylate (PMMA). Preferably, the first polymer is PVDF-HFP, the PVDF-HFP overcomes the defects of high crystallinity and high membrane brittleness of PVDF, and has good electrolyte absorption capacity and excellent electrochemical performance, so that the obtained high-temperature-resistant polymer electrolyte membrane has better performance.
Preferably, the organic solvent comprises one or more of N-methylpyrrolidone (NMP), N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), Acetonitrile (ACN), hexamethylphosphoric triamide (HMPA). The organic solvent in the present invention is required not only as a dispersion solution of the first polymer but more importantly as a dispersion solution and a reaction system of the aromatic diacid chloride and the aromatic diamine. Therefore, it is necessary to meet the above requirements in selecting the organic solvent, and more preferably, the organic solvent is NMP, DMAC, or HMPA.
As described above, the organic solvent is required not only as a dispersion solution of the first polymer, the aromatic diacid chloride and the aromatic diamine but also as a reaction system of the aromatic diacid chloride and the aromatic diamine. The amount of the organic solvent used will directly affect the degree of dissolution and dispersion of the first polymer, the aromatic diacid chloride, and the aromatic diamine, and the degree of polymerization of the aromatic polyamide obtained by in situ polymerization of the aromatic diacid chloride and the aromatic diamine. Therefore, the amount of the organic solvent added has a great influence on the properties of the finally obtained polymer electrolyte membrane. Preferably, in step S1, the first mixed solution includes 1 to 15% of the first polymer and 85 to 99% of the organic solvent. In the solution system, the first polymer can be fully dispersed and dissolved, and meanwhile, the mutual collision probability of the aromatic diacid chloride and the aromatic diamine is proper, so that the aromatic polyamide with proper molecular weight can be obtained through in-situ polymerization. On the contrary, if the content of the organic solvent in the first mixed solution is too low, the aromatic diacid chloride and the aromatic diamine are subjected to side reaction, and the polymer chain is easily terminated due to violent reaction, so that the aromatic polyamide with high molecular weight cannot be obtained, and the aromatic polyamide and the first polymer cannot be fully mixed and interpenetrated to form a three-dimensional network structure with uniform texture. More preferably, the first mixture comprises 1-10% of the first polymer and 90-99% of the organic solvent.
In step S2, preferably, the lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium bistrifluoromethanesulfonylimide (LiTFSI), lithium difluorooxalatoborate (LiODFB), lithium perchlorate (LiClO)4) One or more of (a). More preferably, the lithium salt is LiPF6，LiPF6The electrolyte has higher conductivity, strong electrochemical stability and better comprehensive performance than other lithium salts. The amount of the lithium salt added will directly affect the polymerizationThe ion conductivity of the compound electrolyte membrane is preferably 0.5-5% by mass of the first mixed solution. More preferably, the amount of the lithium salt added is 0.5-2% of the mass of the first mixed solution.
In step S3, preferably, the aromatic diacid chloride is terephthaloyl chloride and/or isophthaloyl chloride; the aromatic diamine is p-phenylenediamine and/or m-phenylenediamine. The aromatic diacid chlorides and aromatic diamines are not limited to those listed above. The aromatic diacid chloride and the aromatic diamine are subjected to in-situ polymerization reaction in an organic solvent system to obtain aromatic polyamide, and finally the polymer electrolyte membrane with an interpenetrating network structure of aromatic polyamide molecular chains and polymer molecular chains is obtained. Therefore, the manufacturing process in step S3 is particularly important.
First, the order of addition of the aromatic diacid chloride and the aromatic diamine will affect the properties of the finally obtained aromatic polyamide. Preferably, the aromatic diacid chloride is added first, after it has dissolved, the aromatic diamine is added. If the aromatic diamine is added firstly, the aromatic diamine can react with the aromatic diacid chloride added later in the solution quickly, so that the molecular weight of the prepared aromatic diacid chloride is low, the winding and inserting effect of the aromatic diacid chloride and the first polymer is influenced, and the high-temperature resistance of the obtained aromatic diacid chloride is influenced. Therefore, the invention adopts the steps of firstly adding the aromatic diacid chloride, and then adding the aromatic diamine after the aromatic diacid chloride is dissolved.
The amount of the aromatic diamine and the aromatic diacid chloride added will then have an effect on the resulting polymer electrolyte membrane. The molar ratio of the monomers in the polymerization reaction is influenced by the adding amount of the aromatic diamine and the aromatic diacid chloride, and according to the principle of Flory polycondensation, the formula polymerization degree P is (1+ r)/(1-r), r represents the molar ratio of the two monomers, and when the value of r is close to 1, the corresponding polymerization degree is larger, and the eta of the obtained polymer is largerinhThe larger. Accordingly, the aromatic polyamide obtained in the present invention has a large degree of polymerization, and on the one hand, the three-dimensional network structure obtained by interpenetration thereof with the first polymer is more stable, and two moleculesThe stronger the interaction between the chains. On the other hand, the larger the degree of polymerization of the aromatic polyamide obtained by in-situ polymerization, the larger the mechanical strength and high-temperature resistance thereof are within a certain range. Therefore, the control of the addition amount of the aromatic diamine and the aromatic diacid chloride has an important influence on the obtainment of the polymer electrolyte membrane with high mechanical strength and good temperature resistance. Preferably, the amount of the aromatic diamine added is 40 to 60% of the amount of the aromatic diacid chloride added. Under such conditions, the molar ratio of the aromatic diamine to the aromatic diacid chloride approaches 1, and the aromatic diacid chloride monomer is slightly in excess in order to compensate for negative effects in many respects, such as side reactions occurring in the reaction. More preferably, the amount of the aromatic diamine added is 50 to 60 percent of the amount of the aromatic diacid chloride added.
In addition, in the reaction process of the aromatic diamine and the aromatic diacid chloride, the reaction temperature and the reaction time have certain influence on the obtained polymer electrolyte membrane. Specifically, the reaction temperature is preferably-15 to 0 ℃. The reaction activity of the aromatic diamine and the aromatic diacid chloride is high, and the two monomers can be quickly polymerized only by being added into a solvent for contact. However, this reaction is not expected, and thus the reaction process is difficult to control, and a polymer electrolyte membrane having a uniform structure cannot be obtained. The polymerization of a low-temperature solution at the temperature of-15-0 ℃ is adopted to reduce the activity of two reaction monomers and prevent the two monomers from imploding and generating a large number of side reactions during the polymerization reaction, so that on one hand, the method is favorable for obtaining the aromatic polyamide with high polymerization degree, on the other hand, the method is favorable for fully interpenetrating the aromatic polyamide and the first polymer to obtain the polymer electrolyte membrane with uniform structure at each part. Preferably, the reaction time is 1-6 h. Sufficient reaction time facilitates the molecular weight increase of the aromatic polyamide and also facilitates the sufficient interpenetration of the aromatic polyamide with the first polymer.
Finally, the influence of the organic solvent system on the resulting polymer electrolyte membrane is not negligible. In the present invention, the organic solvent is not only required to disperse the first polymer but also required to be a reaction system and a dissolution system of the aromatic polyamide. General purposePreferably, the organic solvent is one or more of HMPA, NMP, DMAC, DMF. More preferably, calcium chloride or lithium chloride is added into the organic solvent to obtain NMP-CaCl2、DMAC-CaCl2Or a composite solvent system such as DMAC-LiCl. The purpose of dissolving aid can be achieved by adding a certain amount of calcium chloride or lithium chloride. The proper amount of cosolvent can prevent the aromatic polyamide generated by the polymerization reaction from forming gel, and is favorable for finally forming the polymer electrolyte membrane with an interpenetrating three-dimensional structure. If the added cosolvent is excessive and is easy to absorb water, the introduced water molecules can generate unnecessary side reactions with the polymerized monomer, and the polymerization degree of the obtained aromatic polyamide is influenced. Preferably, the addition amount of the calcium chloride or the lithium chloride is 3-9% of the mass of the organic solvent.
In conclusion, in step S3, the aromatic polyamide with a high degree of polymerization is obtained by controlling the preparation process, and the aromatic polyamide with a high degree of polymerization interpenetrates with the molecular chain of the first polymer, so that the polymer electrolyte membrane with a uniform structure at each position is obtained, and the mechanical strength and the ionic conductivity are improved.
In step S4, the polymer electrolyte slurry is coated on a substrate to obtain a polymer electrolyte wet film. Specifically, the polymer electrolyte slurry was coated on a glass plate using a fixed doctor blade to obtain a polymer electrolyte wet film.
In step S5, the wet polymer electrolyte membrane is dried to obtain a finished product. The drying conditions will affect the properties of the finally obtained polymer electrolyte membrane, and preferably, the drying temperature is 50-90 ℃ and the drying time is 4-8 h.
In conclusion, the high-temperature-resistant polymer electrolyte membrane is obtained according to the method, has a three-dimensional structure, and is mainly formed by mutually interpenetration of an aromatic polyamide molecular chain obtained by in-situ polymerization and a first polymer molecular chain. The high-temperature-resistant polymer electrolyte membrane has the advantages of good mechanical strength, stable structure, high heat resistance and excellent film forming performance. The polymer electrolyte membrane obtained by the invention has excellent processing and film-forming properties, and has certain flexibility while keeping certain rigidity. The rigid aromatic polyamide molecular chain and the soft polymer molecular chain form an interpenetrating network structure, so that the characteristics of high heat resistance, structural stability and the like of the aromatic polyamide are reserved, and the high ion transmission capability of the polymer is achieved.
The invention is further illustrated by the following specific examples:
example 1
A preparation method of a high-temperature-resistant polymer electrolyte membrane comprises the following steps:
s1, weighing 1g of PVDF-HFP, and dissolving in 30g of NMP to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 2.2g of terephthaloyl chloride into the second mixed solution, adding 1.2g of p-phenylenediamine after the terephthaloyl chloride is dissolved, stirring, and reacting at 0 ℃ for 2 hours to obtain polymer electrolyte slurry;
wherein, calcium chloride is also added into NMP; the amount of calcium chloride added was 0.9 g.
S4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet membrane of the polymer electrolyte at 50 ℃ for 8h to obtain a finished product.
Example 2
A preparation method of a high-temperature-resistant polymer electrolyte membrane comprises the following steps:
s1, weighing 2g of PVDF-HFP, and dissolving in 30g of NMP to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 2.2g of terephthaloyl chloride into the second mixed solution, adding 1.2g of p-phenylenediamine after the terephthaloyl chloride is dissolved, stirring, and reacting at 0 ℃ for 2 hours to obtain polymer electrolyte slurry;
wherein, calcium chloride is also added into NMP; the amount of calcium chloride added was 0.9 g.
S4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 70 ℃ for 5 hours to obtain a finished product.
Example 3
A preparation method of a high-temperature-resistant polymer electrolyte membrane comprises the following steps:
s1, weighing 3g of PVDF-HFP, and dissolving in 30g of NMP to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 2.2g of terephthaloyl chloride into the second mixed solution, adding 1.2g of p-phenylenediamine after the terephthaloyl chloride is dissolved, stirring, and reacting at 0 ℃ for 2 hours to obtain polymer electrolyte slurry;
wherein, calcium chloride is also added into NMP; the amount of calcium chloride added was 1.0 g.
S4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 90 ℃ for 4h to obtain a finished product.
Example 4
A preparation method of a high-temperature-resistant polymer electrolyte membrane comprises the following steps:
s1, weighing 2g of PVDF, and dissolving in 30g of NMP to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 2.2g of terephthaloyl chloride into the second mixed solution, adding 1.2g of p-phenylenediamine after the terephthaloyl chloride is dissolved, stirring, and reacting at 0 ℃ for 2 hours to obtain polymer electrolyte slurry;
wherein, calcium chloride is also added into NMP; the amount of calcium chloride added was 0.9 g.
S4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet membrane of the polymer electrolyte at 50 ℃ for 8h to obtain a finished product.
Example 5
A preparation method of a high-temperature-resistant polymer electrolyte membrane comprises the following steps:
s1, weighing 1g of PVDF, and dissolving in 30g of DMAC to obtain a first mixed solution;
s2, adding 0.155g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 3g of isophthaloyl dichloride into the second mixed solution, adding 1.5g of m-phenylenediamine after the isophthaloyl dichloride is dissolved, stirring, and reacting at-15 ℃ for 1h to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet membrane of the polymer electrolyte at 50 ℃ for 8h to obtain a finished product.
Example 6
A preparation method of a high-temperature-resistant polymer electrolyte membrane comprises the following steps:
s1, weighing 2g of PEO and dissolving in 30g of acetonitrile to obtain a first mixed solution;
s2, adding 1.5g LiClO to the first mixed solution4Obtaining a second mixed solution;
s3, adding 2.2g of isophthaloyl dichloride into the second mixed solution, adding 1.2g of m-phenylenediamine after the isophthaloyl dichloride is dissolved, stirring, and reacting at 0 ℃ for 6 hours to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet membrane of the polymer electrolyte at 50 ℃ for 8h to obtain a finished product.
Example 7
A preparation method of a high-temperature-resistant polymer electrolyte membrane comprises the following steps:
s1, weighing 2g of PMMA and dissolving in 30g of DMAC to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 2.2g of terephthaloyl chloride into the second mixed solution, adding 1.2g of p-phenylenediamine after the terephthaloyl chloride is dissolved, stirring, and reacting at 0 ℃ for 2 hours to obtain polymer electrolyte slurry;
wherein, lithium chloride is also added into DMAC; the amount of lithium chloride added was 2.7 g.
S4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
and S5, drying the wet polymer electrolyte membrane at 60 ℃ for 5 hours to obtain a finished product.
Comparative example 1
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 2g of PEO and dissolving in 30g of acetonitrile to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution to obtain a second mixed solution;
and S3, coating the second mixed solution on a base material, and drying at 60 ℃ for 5 hours to obtain a finished product.
Comparative example 2
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 2g of PVDF-HFP, and dissolving in 30g of NMP to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution to obtain a second mixed solution;
and S3, coating the second mixed solution on a base material, and drying at 60 ℃ for 5 hours to obtain a finished product.
Comparative example 3
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 2g of PVDF-HFP, and dissolving in 30g of NMP to obtain a first mixed solution;
s2, adding 0.6g of LiTFSI into the first mixed solution, and after completely dissolving, adding 2g of poly (m-phenylene isophthalamide) (PMIA) short fibers to obtain a second mixed solution;
and S3, coating the second mixed solution on a base material, and drying at 60 ℃ for 5 hours to obtain a finished product.
The polymer electrolyte membranes prepared in examples 1 to 7 and comparative examples 1 to 3 were subjected to heat shrinkage performance test and ionic conductivity test, wherein the test temperature of the heat shrinkage performance test was 150 ℃, the test time was 1 hour, and the test results are shown in fig. 1. The heat shrinkage rate of the high-temperature resistant polymer electrolyte membrane provided by the invention is smaller than that of a single polymer electrolyte membrane, and the high-temperature resistant polymer electrolyte membrane shows good heat resistance.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a high-temperature-resistant polymer electrolyte membrane is characterized by comprising the following steps:
s1, dissolving the first polymer in an organic solvent to obtain a first mixed solution;
s2, adding lithium salt into the first mixed solution to obtain a second mixed solution;
s3, adding aromatic diacid chloride into the second mixed solution, adding aromatic diamine after the aromatic diacid chloride is dissolved, and stirring and reacting completely to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the wet membrane of the polymer electrolyte to obtain a finished product;
the addition amount of the first polymer: the addition amount of aromatic diacid chloride: the addition amount of the aromatic diamine is (1-3): (2 to 3) and (1 to 2).
2. The method for preparing a high temperature resistant polymer electrolyte membrane according to claim 1, wherein the aromatic diacid chloride is terephthaloyl chloride and/or isophthaloyl chloride; the aromatic diamine is p-phenylenediamine and/or m-phenylenediamine.
3. The method for preparing a high temperature resistant polymer electrolyte membrane according to claim 2,
the first polymer comprises one or the combination of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polypropylene carbonate and polymethyl methacrylate:
the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide and lithium difluorooxalato borate;
the organic solvent comprises one or more of N-methyl pyrrolidone, N-dimethyl acetamide, N-dimethyl formamide, acetonitrile and hexamethyl phosphoric triamide.
4. The method for producing a high-temperature resistant polymer electrolyte membrane according to claim 1, wherein in step S1, the first mixed solution contains 1 to 15% of the first polymer and 85 to 99% of the organic solvent.
5. The method for preparing a high temperature resistant polymer electrolyte membrane according to claim 4, wherein in step S1, calcium chloride or lithium chloride is further added to the organic solvent; the addition amount of the calcium chloride or the lithium chloride is 3-9% of the mass of the organic solvent.
6. The method for producing a high-temperature resistant polymer electrolyte membrane according to claim 1, wherein in step S2, the amount of the lithium salt added is 0.5 to 5% by mass of the first mixed solution.
7. The method for preparing a high temperature resistant polymer electrolyte membrane according to claim 6, wherein the amount of the aromatic diamine added is 40% to 60% of the amount of the aromatic diacid chloride added in step S3.
8. The method for preparing a high temperature resistant polymer electrolyte membrane according to claim 1, wherein in the step S3, during the reaction: the reaction temperature is-15 to 0 ℃, and the reaction time is 1 to 6 hours.
9. The method of preparing a high temperature resistant polymer electrolyte membrane according to claim 1, wherein the drying temperature is 50 ℃ to 90 ℃ and the drying time is 4 to 8 hours in step S5.
10. A high temperature resistant polymer electrolyte membrane prepared by the preparation method of the high temperature resistant polymer electrolyte membrane according to claims 1-9.
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