CN114006032A - Solid polymer electrolyte membrane and manufacturing method thereof - Google Patents
Solid polymer electrolyte membrane and manufacturing method thereof Download PDFInfo
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- CN114006032A CN114006032A CN202111094481.3A CN202111094481A CN114006032A CN 114006032 A CN114006032 A CN 114006032A CN 202111094481 A CN202111094481 A CN 202111094481A CN 114006032 A CN114006032 A CN 114006032A
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 121
- 239000012528 membrane Substances 0.000 title claims abstract description 81
- 239000007787 solid Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 58
- 239000004760 aramid Substances 0.000 claims abstract description 46
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 46
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- -1 polypropylene carbonate Polymers 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- 238000007385 chemical modification Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 5
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003190 poly( p-benzamide) Polymers 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 description 13
- 229910052809 inorganic oxide Inorganic materials 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 229920006231 aramid fiber Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 210000003746 feather Anatomy 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 210000001724 microfibril Anatomy 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- OSVNIDFTIILWFP-UHFFFAOYSA-N 7-azabicyclo[2.2.1]hepta-1,3,5-triene-7-carbaldehyde Chemical compound O=CN1C2=CC=C1C=C2 OSVNIDFTIILWFP-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003806 hair structure Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a preparation method of a solid 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 polyamide pulp into the second mixed solution, and dispersing uniformly 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 polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of first polymer, 80-95% of organic solvent, 1-10% of lithium salt and 1-15% of aromatic polyamide pulp. Correspondingly, the invention also provides the solid polymer electrolyte membrane prepared by the method, which has the advantages of good mechanical strength, stable structure, high heat resistance and excellent membrane forming property.
Description
Technical Field
The invention relates to the technical field of solid batteries, in particular to a solid polymer electrolyte membrane and a manufacturing 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. The use of solid electrolytes instead of electrolytes and separators can fundamentally eliminate the above safety problems. 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 its development and application due to low ionic conductivity, poor mechanical strength and heat resistance, etc.
The polymer electrolyte is mainly prepared by dissolving polymer (PEO, PVDF, PVDF-HFP, PPC, PMMA, etc.) in solvent (NMP, DMAC, DMF, ACN, acetone), 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. The polymer electrolyte membrane has poor mechanical strength and heat resistance, the membrane forming quality is general, and when the battery is out of control due to heat, the electrolyte membrane is easy to deform in structure, so that the positive electrode and the negative electrode are triggered to generate short circuit, 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 cycle performance are severely damaged. One of the reasons for the above problems is that the compatibility of inorganic oxide and polymer is poor, and the dispersion is uneven, resulting in poor mechanical strength and heat resistance of the existing polymer system.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a solid polymer electrolyte membrane, which adopts aromatic polyamide pulp with excellent heat resistance as a reinforcing filler to obtain the solid polymer electrolyte membrane with excellent performance.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a solid polymer electrolyte membrane having good heat resistance and high ionic conductivity.
In order to solve the above technical problems, the present invention provides a method for preparing a solid 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 polyamide pulp into the second mixed solution, and dispersing uniformly 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 polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of first polymer, 80-95% of organic solvent, 1-10% of lithium salt and 1-15% of aromatic polyamide pulp.
Preferably, the aromatic polyamide pulp is one or a combination of poly (p-phenylene terephthalamide) pulp, poly (m-phenylene isophthalamide) pulp and poly (p-benzamide) pulp;
the specific surface area of the aromatic polyamide pulp is 1-12 m2/g。
Preferably, the first polymer comprises one or a combination of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polypropylene carbonate and polymethyl methacrylate.
Preferably, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluorooxalato borate.
Preferably, the organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, acetonitrile, acetone, hexamethylphosphoric triamide.
Preferably, in S3, the aromatic polyamide pulp is subjected to a pretreatment including ultrasonic pre-impregnation and/or chemical modification.
Preferably, the ultrasonic pre-dipping conditions are: the ultrasonic treatment power is 500-800 w, and the treatment time is 5-15 min.
Preferably, the chemical modification conditions are: treating in 10-15% sodium hydroxide solution for 2-4 h.
Preferably, in the step S5, the drying temperature is 60-100 ℃, and the drying time is 5-25 h.
The invention also provides the solid polymer electrolyte membrane prepared by the preparation method.
The implementation of the invention has the following beneficial effects:
1. the preparation method of the solid polymer electrolyte membrane provided by the invention uses the aromatic polyamide pulp with rich root-like special structure and good high-temperature resistance to replace the existing inorganic oxide filler, and prepares the polymer electrolyte membrane with high heat resistance, good mechanical strength and high ionic conductivity under the condition of not using inorganic matters and a support body. The aromatic polyamide pulp is added into the existing polymer electrolyte, so that the mechanical strength and the heat resistance of the polymer electrolyte membrane are improved on one hand, and on the other hand, the specific surface area of the pulp with rich feather root structures is large, the interface between the pulp and the polymer is increased, and more ion transmission channels are promoted; but also greatly reduces the crystallinity of the polymer, thereby greatly improving the ionic conductivity of the polymer electrolyte membrane.
2. In the prior art, the polymer electrolyte membrane is prepared by dissolving and mixing the aromatic polyamide fiber and the polymer, the aromatic polyamide pulp and the polymer are directly mixed, and the adding method is simple, quick and efficient. Compared with the inorganic oxide filler, the aromatic polyamide pulp has better compatibility with the polymer and more uniform dispersion. And the specific surface area of the aromatic polyamide pulp is much larger than that of the inorganic oxide, so that the crystallinity of the polymer is greatly reduced, more polymer-pulp interfaces are promoted to be generated, more ion transmission channels are provided, and the ionic conductivity of the polymer electrolyte is greatly improved.
Drawings
FIG. 1 is a graph showing a comparison of test performances of polymer electrolyte membranes obtained in examples 1 to 6 of the present invention and comparative examples 1 to 4.
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 invention provides a preparation method of a solid 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 polyamide pulp into the second mixed solution, and dispersing uniformly 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 polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of first polymer, 80-95% of organic solvent, 1-10% of lithium salt and 1-15% of aromatic polyamide pulp.
The preparation method of the solid polymer electrolyte membrane provided by the invention uses the aromatic polyamide pulp with rich root-like special structure and good high temperature resistance to replace the existing inorganic oxide filler, and prepares the polymer electrolyte membrane with high heat resistance, good mechanical strength and high ionic conductivity under the condition of not using inorganic matters and a support body. The aromatic polyamide pulp is added into the existing polymer electrolyte, so that the mechanical strength and the heat resistance of the polymer electrolyte membrane are improved on one hand, and on the other hand, the specific surface area of the pulp with rich feather root structures is large, the interface between the pulp and the polymer is increased, and more ion transmission channels are promoted; but also greatly reduces the crystallinity of the polymer, thereby greatly improving the ionic conductivity of the polymer electrolyte membrane.
In the prior art, the polymer electrolyte membrane is prepared by dissolving and mixing the aromatic polyamide fiber and the polymer, the invention directly mixes the aromatic polyamide pulp and the polymer, and the adding method is simple, quick and efficient. Compared with the inorganic oxide filler, the aromatic polyamide pulp has better compatibility with the polymer and more uniform dispersion. And the specific surface area of the aromatic polyamide pulp is much larger than that of the inorganic oxide, so that the crystallinity of the polymer is greatly reduced, more polymer-pulp interfaces are promoted to be generated, more ion transmission channels are provided, and the ionic conductivity of the polymer electrolyte is greatly improved.
In addition, in the prior art, the aromatic polyamide pulp or the aromatic polyamide fiber is made into a battery separator or a support to improve the heat resistance, but the technical method cannot further improve the ionic conductivity of the solid electrolyte. The invention mixes the pulp with rich feather root hair structure as the filler in the polymer, which can provide more ion transmission channels for the solid electrolyte, reduce the crystallinity of the polymer and further greatly improve the ionic conductivity of the polymer electrolyte membrane.
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 solid 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), acetone, hexamethylphosphoric triamide (HMPA). The organic solvent in the present invention is required not only as a dispersion solution of the first polymer but also as a dispersion solution of the aromatic polyamide pulp. 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.
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 LiTFSI, the LiTFSI has proper conductivity, high thermal stability and electrochemical stability and small probability of side reaction.
In step S3, the present invention adds a high temperature resistant aromatic polymer fiber pulp with a special structure rich in feather root hair to the existing polymer electrolyte system, and the prepared electrolyte membrane has high strength, high heat resistance and greatly improved ionic conductivity without adding inorganic oxides and composite supports.
Preferably, the aromatic polyamide pulp is one or a combination of poly (p-phenylene terephthalamide) (PPTA) pulp, poly (m-phenylene isophthalamide) (PMIA) pulp and poly (p-phenylene formamide) (PBA) pulp.
Aramid is a generic name for high molecular polymers whose molecules are composed of aromatic rings and amide group repeating chain links. The aramid fiber has a relative density of 1.33 to 1.45 and a thermal decomposition temperature of 371 to 500 ℃, and is a high polymer having the highest heat resistance known so far. The aramid pulp has a density of 1.41 g-cm-3Is slightly smaller than aramid fiber, has a plush surface, is free from generation of micro-fiber and rich in hairiness, and has axial tail end fibrillating into a needle tipThe aramid fiber has a large surface area, and can reach more than 10 times of the aramid fiber. The specific surface area of the aromatic polyamide pulp is too small, the bonding interface between the aromatic polyamide pulp and the polymer is small, and a sufficient ion transport channel cannot be generated, thereby decreasing the ionic conductivity of the polymer electrolyte membrane; on the contrary, the aromatic polyamide pulp having too large specific surface area greatly reduces the crystallinity of the polymer, resulting in a decrease in the mechanical strength of the polymer electrolyte membrane. Preferably, the specific surface area of the aromatic polyamide pulp is 1-12 m2/g。
The aromatic polyamide pulp has better dispersion performance than aramid fiber, has good toughness and is not easy to break in the mixing processing process. Therefore, the aromatic polyamide pulp is more easily dispersed uniformly in the polymer electrolyte system. Further, in order to improve the dispersion property of the aromatic polyamide pulp in the polymer electrolyte system, it is preferable that the aromatic polyamide pulp is subjected to a pretreatment including ultrasonic prepreg and/or chemical modification in the step S3.
Preferably, the ultrasonic pre-dipping conditions are: the ultrasonic treatment power is 500-800 w, and the treatment time is 5-15 min. The dispersion performance of the aromatic polyamide pulp subjected to ultrasonic impregnation in a polymer electrolyte system is improved, and the cavitation effect in the ultrasonic treatment propagation process generates microcracks on the surface of the pulp, increases the specific surface area, enlarges the interface between the pulp and a polymer and promotes more ion transmission channels; but also greatly reduces the crystallinity of the polymer, thereby greatly improving the ionic conductivity of the polymer electrolyte membrane.
Preferably, the chemical modification conditions are: treating in 10-15% sodium hydroxide solution for 2-4 h. The aromatic polyamide pulp is pretreated by alkali liquor under the condition, so that the mechanical strength of the polymer electrolyte membrane can be improved to a certain extent. The aramid pulp contains a large number of microfibrils, the surfaces of the microfibrils contain a large number of amide groups, and the amide groups on the surface parts of the fibers can be broken through the treatment of sodium hydroxide alkali liquor to form more active end groups, so that the surface activity of the pulp is improved. The modified aromatic polyamide pulp and the polymer electrolyte matrix have more hydrogen bond functions, so that the mechanical strength of the polymer electrolyte membrane is improved.
In step S4, the polymer electrolyte slurry is coated on a substrate to obtain a wet polymer electrolyte membrane. Specifically, the polymer electrolyte slurry was coated on a glass plate using a fixed doctor blade to obtain a wet polymer electrolyte membrane.
In step S5, the wet polymer electrolyte membrane is dried to obtain a finished product. The drying conditions affect the performance of the finally obtained polymer electrolyte membrane, and preferably, the drying temperature is 60-100 ℃, and the drying time is 5-25 h.
In summary, the present invention provides a solid polymer electrolyte membrane comprising a high-temperature-resistant aromatic polyamide pulp having a rich root-like specific structure, instead of the conventional inorganic oxide filler, and having excellent properties of high heat resistance, mechanical strength and ionic conductivity without containing inorganic materials and a support.
The invention is further illustrated by the following specific examples:
example 1
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1g of PVDF-HFP, and dissolving in 13g of NMP to obtain a first mixed solution;
s2, adding 0.4g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 0.6g of PPTA pulp into the second mixed solution, dispersing at a high speed of 1000rpm for 2 hours, and obtaining polymer electrolyte slurry after the dispersion;
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 24h to obtain a finished product.
Example 2
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1g of PVDF-HFP, and dissolving in 13g of NMP to obtain a first mixed solution;
s2, adding 0.4g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 1.6g of PPTA pulp into the second mixed solution, dispersing at a high speed of 1000rpm for 2 hours, and obtaining polymer electrolyte slurry after the dispersion;
before the PPTA pulp is added into the second mixed solution, carrying out ultrasonic pre-impregnation on the PPTA pulp, wherein the ultrasonic pre-impregnation conditions are as follows: the ultrasonic treatment power is 600w, and the treatment time is 10 min.
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 20h to obtain a finished product.
Example 3
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1.5g of PVDF-HFP, and dissolving in 13g of DMAC to obtain a first mixed solution;
s2, adding 0.4g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 2.5g of PMIA pulp into the second mixed solution, dispersing at a high speed of 1000rpm for 2 hours, and obtaining polymer electrolyte slurry after the PMIA pulp is dispersed;
before the PPTA pulp is added into the second mixed solution, performing alkali liquor preimpregnation on the PPTA pulp, wherein the alkali liquor preimpregnation conditions are as follows: the mixture is treated in 10% sodium hydroxide solution for 2 h.
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 15h to obtain a finished product.
Example 4
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1g of PVDF, and dissolving in 13g of NMP to obtain a first mixed solution;
s2, adding 0.4g LiPF into the first mixed solution6Obtaining a second mixed solution;
s3, adding 1.6g of PMIA pulp into the second mixed solution, dispersing at a high speed of 1000rpm for 2 hours, and obtaining polymer electrolyte slurry after the PMIA pulp is dispersed;
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 100 ℃ for 8h to obtain a finished product.
Example 5
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1g of PEO and dissolving in 13g of ACN to obtain a first mixed solution;
s2, adding 0.4g of LiTFSI into the first mixed solution to obtain a second mixed solution;
s3, adding 1.6g of PPTA pulp into the second mixed solution, dispersing at a high speed of 1000rpm for 2 hours, and obtaining polymer electrolyte slurry after the dispersion;
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 24h to obtain a finished product.
Example 6
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1g of PMMA and dissolving in 13g of acetone to obtain a first mixed solution;
s2, adding 0.4g LiClO into the first mixed solution4Obtaining a second mixed solution;
s3, adding 1.6g of PPTA pulp into the second mixed solution, dispersing at a high speed of 1000rpm for 2 hours, and obtaining polymer electrolyte slurry after the dispersion;
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 24h to obtain a finished product.
Comparative example 1
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 1g of PVDF-HFP, and dissolving in 13g of NMP to obtain a first mixed solution;
s2, adding 0.4g 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 80 ℃ for 24h to obtain a finished product.
Comparative example 2
A method of preparing a polymer electrolyte membrane comprising the steps of:
s1, weighing 1g of PVDF-HFP, and dissolving in 13g of NMP to obtain a first mixed solution;
s2, adding 0.4g of LiTFSI and 1.6gAl into the first mixed solution2O3Obtaining a second mixed solution;
and S3, coating the second mixed solution on a base material, and drying at 80 ℃ for 24h to obtain a finished product.
Comparative example 3
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1g of PEO and dissolving in 13g of ACN to obtain a first mixed solution;
s2, adding 0.4g of LiTFSI and 1.6gAl into the first mixed solution2O3Obtaining a second mixed solution;
and S3, coating the second mixed solution on a base material, and drying at 80 ℃ for 24h to obtain a finished product.
Comparative example 4
A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, weighing 1g of PMMA and dissolving in 13g of acetone to obtain a first mixed solution;
s2, adding 0.4g LiClO into the first mixed solution4And 1.6gAl2O3Obtaining a second mixed solution;
and S3, coating the second mixed solution on a base material, and drying at 80 ℃ for 24h to obtain a finished product.
The polymer electrolyte membranes obtained in examples 1 to 6 and comparative examples 1 to 4 were subjected to tests for heat shrinkability and ionic conductivity at a test temperature of 150 ℃ for a test time of 1 hour.
The polymer electrolyte membranes prepared in examples 1 to 6 and comparative examples 1 to 4 were cut into disks having a diameter of 100mm, placed in an oven at 150 ℃ for 1 hour, taken out and the diameter d of the disk was measured again, and the thermal shrinkage of the electrolyte membrane was calculated using formula 1.
Formula 1 is a calculation formula of heat shrinkage rate
The polymer electrolyte membranes prepared in examples 1 to 6 and comparative examples 1 to 4 were assembled into a stainless steel sheet/electrolyte membrane/stainless steel sheet button cell, and the electrochemical impedance spectrum of the electrolyte membrane was measured by an ac impedance method using an electrochemical workstation. The thickness h and the diameter d of the polymer electrolyte sheet are measured by a thickness gauge, R is the impedance of the polymer electrolyte membrane, and the ionic conductivity is calculated by adopting a formula 2.
σ＝h/(R·π(d/2)^2)
Equation 2 is an ion conductivity calculation equation
The test results are shown in fig. 1, the proportions of PPTA pulp in the polymer electrolyte in the electrolyte slurries of examples 1 to 3 were 4%, 10%, and 14.8%, respectively, and the proportions of PPTA pulp in examples 4 to 6 were 10%. The heat shrinkage rates of the examples are all smaller than those of the comparative examples, and example 2 has the smallest heat shrinkage rate and the best 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 method for producing a solid 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 polyamide pulp into the second mixed solution, and dispersing uniformly 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 polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of first polymer, 80-95% of organic solvent, 1-10% of lithium salt and 1-15% of aromatic polyamide pulp.
2. The method for producing a solid polymer electrolyte membrane according to claim 1, wherein the aromatic polyamide pulp is one or a combination of poly (p-phenylene terephthalamide) pulp, poly (m-phenylene isophthalamide) pulp and poly (p-benzamide) pulp;
the specific surface area of the aromatic polyamide pulp is 1-12 m2/g。
3. The method of manufacturing a solid polymer electrolyte membrane according to claim 1, wherein the first polymer comprises one or a combination of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polypropylene carbonate, and polymethyl methacrylate.
4. The method of making a solid polymer electrolyte membrane according to claim 1, wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, lithium difluorooxalato borate.
5. The method of claim 1, wherein the organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, acetonitrile, acetone, hexamethylphosphoric triamide.
6. The method for producing a solid polymer electrolyte membrane according to claim 1, wherein in S3, the aromatic polyamide pulp is subjected to pretreatment including ultrasonic prepreg and/or chemical modification.
7. The method for producing a solid polymer electrolyte membrane according to claim 6, wherein the ultrasonic preimpregnation conditions are: the ultrasonic treatment power is 500-800 w, and the treatment time is 5-15 min.
8. The method for producing a solid polymer electrolyte membrane according to claim 6, wherein the chemical modification conditions are: treating in 10-15% sodium hydroxide solution for 2-4 h.
9. The method for preparing a solid polymer electrolyte membrane according to claim 1, wherein the drying temperature is 60 ℃ to 100 ℃ and the drying time is 5 to 25 hours in step S5.
10. A solid polymer electrolyte membrane produced by the method for producing a solid polymer electrolyte membrane according to claims 1 to 9.
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| CN116742107A (en) * | 2023-07-31 | 2023-09-12 | 武汉中科先进材料科技有限公司 | Composite solid electrolyte membrane for lithium metal negative electrode and preparation method thereof |
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