CN114006032B - Solid polymer electrolyte membrane and manufacturing method thereof - Google Patents
Solid polymer electrolyte membrane and manufacturing method thereof Download PDFInfo
- Publication number
- CN114006032B CN114006032B CN202111094481.3A CN202111094481A CN114006032B CN 114006032 B CN114006032 B CN 114006032B CN 202111094481 A CN202111094481 A CN 202111094481A CN 114006032 B CN114006032 B CN 114006032B
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- electrolyte membrane
- pulp
- mixed solution
- aromatic polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 118
- 239000012528 membrane Substances 0.000 title claims abstract description 65
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 57
- 239000004760 aramid Substances 0.000 claims abstract description 48
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 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
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- -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
- 238000005470 impregnation Methods 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
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 6
- 229910001486 lithium perchlorate Inorganic materials 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
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 description 16
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 13
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 229910052809 inorganic oxide Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 6
- 229920000889 poly(m-phenylene isophthalamide) Polymers 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
- 210000003746 feather Anatomy 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 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
- 229920003190 poly( p-benzamide) Polymers 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification 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
- 235000012431 wafers Nutrition 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001453 impedance spectrum Methods 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
- 239000011159 matrix material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 210000001724 microfibril Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010345 tape casting Methods 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
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a solid polymer electrolyte membrane, which comprises the following steps: s1, dissolving a 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 uniformly dispersing to obtain polymer electrolyte slurry; s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film; s5, drying the polymer electrolyte wet film to obtain a finished product; the polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of a first polymer, 80-95% of an 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 film forming.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a solid-state polymer electrolyte membrane and a manufacturing method thereof.
Background
In order to meet the increasing demands of consumer electronics and electric vehicles for lithium batteries, 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 chemical stability. The use of a solid electrolyte instead of an electrolyte and a separator fundamentally eliminates the above-mentioned safety problems. All-solid-state lithium batteries are classified into three types according to the types of solid electrolytes: polymers, oxides and sulfides. The polymer all-solid-state battery is closest to the existing liquid battery production process, and is an all-solid-state lithium battery which is possible to industrialize at first. However, polymer electrolyte membranes have limited development and application due to low ionic conductivity, poor mechanical strength and heat resistance, and the like.
The polymer electrolyte is prepared by dissolving polymer (PEO, PVDF, PVDF-HFP, PPC, PMMA, etc.) in solvent (NMP, DMAC, DMF, ACN, acetone), and adding lithium salt (LiPF 6 ，LiCLO 4 LiTFSI, etc.), plasticizers or ionic liquids, inorganic oxides, etc., are prepared into electrolyte slurries. The electrolyte slurry is formed into a film by a solution casting method or a knife coating method, and then dried at a high temperature to volatilize the solvent, thereby preparing the polymer electrolyte film. The polymer electrolyte membrane has poor mechanical strength and heat resistance, and the membrane has general membrane forming quality, and when the battery has thermal runaway, the electrolyte membrane is easy to generate structural deformation to cause the contact of the anode and the cathode to generate short circuit, thereby generating safety accidents. Although the heat resistance of the polymer electrolyte membrane can be improved by adding an inorganic oxide or compounding various porous membrane supports, both the uneven dispersion of the oxide and the composite support cause serious decrease in the ionic conductivity of the polymer electrolyte membrane, and the battery capacity and cycle performance are seriously impaired. One of the reasons for the above problems is that the inorganic oxide has poor compatibility with the polymer, and is unevenly dispersed, 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 reinforcing filler to obtain the solid polymer electrolyte membrane with excellent performance.
The technical problem to be solved by the invention is to provide a solid polymer electrolyte membrane which has good heat resistance and high ionic conductivity.
In order to solve the technical problems, the invention provides a preparation method of a solid polymer electrolyte membrane, which comprises the following steps:
s1, dissolving a 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 uniformly dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film to obtain a finished product;
the polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of a first polymer, 80-95% of an 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 (paraphenylene terephthalamide) pulp, poly (m-phenylene isophthalamide) pulp and poly (p-benzamide) pulp;
the specific surface area of the aromatic polyamide pulp is 1-12 m 2 /g。
Preferably, the first polymer comprises one or a combination of polyethylene oxide, polyvinylidene fluoride-co-hexafluoropropylene, polypropylene carbonate, polymethyl methacrylate.
Preferably, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethane sulphonimide, lithium difluorooxalato borate.
Preferably, the organic solvent comprises one or more of N-methylpyrrolidone, N-dimethylacetamide, N-dimethylformamide, acetonitrile, acetone and hexamethylphosphoric triamide.
Preferably, in the step S3, the aromatic polyamide pulp is subjected to a pretreatment including ultrasonic wave pre-impregnation and/or chemical modification.
Preferably, the ultrasonic wave pre-impregnation 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% concentration sodium hydroxide solution for 2-4 hr.
Preferably, in 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 whisker-shaped 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 on one hand, the mechanical strength and heat resistance of the polymer electrolyte membrane are improved, 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; and the crystallinity of the polymer is greatly reduced, so that the ion conductivity of the polymer electrolyte membrane is greatly improved.
2. In the prior art, the polymer electrolyte membrane is prepared by dissolving the aromatic polyamide fibers and mixing the polymer, and the aromatic polyamide pulp and the polymer are directly mixed, so that the adding method is simple, quick and efficient. Compared with inorganic oxide filler, the aromatic polyamide pulp has better compatibility with polymer and more uniform dispersion. And the specific surface area of the aromatic polyamide pulp is much larger than that of 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 ion conductivity of the polymer electrolyte is greatly improved.
Drawings
FIG. 1 is a graph showing the comparison of the test performances of polymer electrolyte membranes obtained in examples 1 to 6 of the present invention and comparative examples 1 to 4.
Detailed Description
The present invention will be described in further detail below in order to make the objects, technical solutions and advantages of the present invention more apparent.
The invention provides a preparation method of a solid polymer electrolyte membrane, which comprises the following steps:
s1, dissolving a 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 uniformly dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film to obtain a finished product;
the polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of a first polymer, 80-95% of an 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 whisker-shaped 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 on one hand, the mechanical strength and heat resistance of the polymer electrolyte membrane are improved, 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; and the crystallinity of the polymer is greatly reduced, so that the ion conductivity of the polymer electrolyte membrane is greatly improved.
In the prior art, the polymer electrolyte membrane is prepared by dissolving the aromatic polyamide fibers and mixing the polymer, and the aromatic polyamide pulp and the polymer are directly mixed, so that the adding method is simple, quick and efficient. Compared with inorganic oxide filler, the aromatic polyamide pulp has better compatibility with polymer and more uniform dispersion. And the specific surface area of the aromatic polyamide pulp is much larger than that of 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 ion conductivity of the polymer electrolyte is greatly improved.
In addition, there are separators or supports for batteries made of aromatic polyamide pulp or aromatic polyamide fibers to improve heat resistance, but this technique cannot further improve ion conductivity of solid electrolytes. According to the invention, the pulp with rich feathers and root structures is used as the filler to be mixed in the polymer, so that more ion transmission channels can be provided for the solid electrolyte, the crystallinity of the polymer is reduced, and the ion conductivity of the polymer electrolyte membrane is greatly improved.
Each step of the production 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), polymethyl methacrylate (PMMA). More preferably, the first polymer is PVDF-HFP, which overcomes the defects of high crystallinity and large film brittleness of PVDF, has good electrolyte absorption capacity and excellent electrochemical performance, and enables the obtained solid polymer electrolyte membrane to have 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, the above requirements are satisfied in selecting the organic solvent, and more preferably, the organic solvent is NMP, DMAC, HMPA.
In step S2, preferably, the lithium salt includes lithium hexafluorophosphate (LiPF 6 ) Lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium difluorooxalato borate(LiODFB), lithium perchlorate (LiClO) 4 ) One or more of the following. More preferably, the lithium salt is LiTFSI, the conductivity of LiTFSI is proper, the thermal stability and the electrochemical stability are high, and the probability of side reaction is low.
In the step S3, the high-temperature resistant aromatic polymer fiber pulp with the special structure rich in feather root and whisker is added into the existing polymer electrolyte system, so that the prepared electrolyte membrane has high strength, high heat resistance and greatly improved ionic conductivity under the condition that inorganic oxide and a composite support are not added.
Preferably, the aromatic polyamide pulp is one or a combination of poly (paraphenylene terephthalamide) (PPTA) pulp, poly (m-phenylene isophthalamide) (PMIA) pulp, and poly (p-benzamide) (PBA) pulp.
The aromatic polyamide is abbreviated as aramid fiber, and is a generic name of high molecular polymers with molecules composed of aromatic rings and amide group repeating units. 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 polymer known to date to have the highest heat resistance. The density of the aramid pulp is 1.41g cm -3 The surface of the fiber is slightly smaller than that of the aramid fiber, the surface of the fiber is in a plush shape, the microfibers are generated from the fiber, the hairiness is abundant, and the fiber axial tail end is fibrillated into a needle point shape, so that the fiber has extremely large surface area which can be 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 less, and a sufficient ion transmission channel cannot be generated, so that the ion conductivity of the polymer electrolyte membrane is reduced; in contrast, the aromatic polyamide pulp having a 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 aromatic polyamide pulp has a specific surface area of 1 to 12m 2 /g。
The aromatic polyamide pulp has better dispersion performance than aramid fibers, has good toughness and is not easy to break in the mixing processing process. Thus, the aromatic polyamide pulp is more easily dispersed uniformly in the polymer electrolyte system. Further, in order to improve the dispersibility of the aromatic polyamide pulp in the polymer electrolyte system, it is preferable that in the step S3, the aromatic polyamide pulp is subjected to a pretreatment including ultrasonic wave prepreg and/or chemical modification.
Preferably, the ultrasonic wave pre-impregnation 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 cavitation in the ultrasonic treatment propagation process enables microcracks to be generated on the surface of the pulp, the specific surface area is increased, the interface between the pulp and a polymer is increased, and more ion transmission channels are promoted; and the crystallinity of the polymer is greatly reduced, so that the ion conductivity of the polymer electrolyte membrane is greatly improved.
Preferably, the chemical modification conditions are: treating in 10-15% concentration sodium hydroxide solution for 2-4 hr. Under the condition, the alkali liquor pretreatment is carried out on the aromatic polyamide pulp, 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 surface of the aramid pulp contains more amide groups, and the amide groups on the surface part of the fibers can be broken through sodium hydroxide alkali liquor treatment to form more active end groups, so that the surface activity of the pulp is improved. The modified aromatic polyamide pulp has more hydrogen bond with the polymer electrolyte matrix, thereby improving the mechanical strength of the polymer electrolyte membrane.
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 polymer electrolyte wet film is dried to obtain a finished product. The drying conditions will affect the properties of the final polymer electrolyte membrane, and preferably the drying temperature is 60-100 ℃ and the drying time is 5-25 hours.
In summary, the present invention provides a solid polymer electrolyte membrane according to the above method, which comprises aromatic polyamide pulp with rich root whisker-like special structure and good high temperature resistance, replaces the existing inorganic oxide filler, and has excellent performances of high heat resistance, good mechanical strength and high ionic conductivity under the condition of not containing inorganic matters and supporting bodies.
The invention is further illustrated by the following examples:
example 1
A method of 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, and dispersing at 1000rpm for 2 hours at high speed to obtain polymer electrolyte slurry after the dispersion;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film at 60 ℃ for 24 hours to obtain a finished product.
Example 2
A method of 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, and dispersing at 1000rpm for 2 hours at high speed to obtain polymer electrolyte slurry after the dispersion;
before the PPTA pulp is added into the second mixed solution, carrying out ultrasonic wave pre-impregnation on the PPTA pulp, wherein the ultrasonic wave pre-impregnation conditions are as follows: the ultrasonic treatment power is 600w and the treatment time is 10min.
S4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film at 70 ℃ for 20 hours to obtain a finished product.
Example 3
A method of 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 PMIA pulp into the second mixed solution, and dispersing at 1000rpm for 2 hours at high speed to obtain polymer electrolyte slurry after the PMIA pulp is dispersed;
before the PPTA pulp is added into the second mixed solution, the PPTA pulp is pre-soaked in alkali liquor, and the pre-soaking conditions of the alkali liquor are as follows: treated in 10% sodium hydroxide solution for 2h.
S4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film at 90 ℃ for 15 hours to obtain a finished product.
Example 4
A method of 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 of LiPF into the first mixed solution 6 Obtaining a second mixed solution;
s3, adding 1.6g PMIA pulp into the second mixed solution, and dispersing at 1000rpm for 2 hours at high speed to obtain 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;
s5, drying the polymer electrolyte wet film at 100 ℃ for 8 hours to obtain a finished product.
Example 5
A method of 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, and dispersing at 1000rpm for 2 hours at high speed to obtain polymer electrolyte slurry after the dispersion;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film at 60 ℃ for 24 hours to obtain a finished product.
Example 6
A method of 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 to the first mixed solution 4 Obtaining a second mixed solution;
s3, adding 1.6g of PPTA pulp into the second mixed solution, and dispersing at 1000rpm for 2 hours at high speed to obtain polymer electrolyte slurry after the dispersion;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film at 70 ℃ for 24 hours to obtain a finished product.
Comparative example 1
A method for 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;
s3, coating the second mixed solution on a substrate, and drying at 80 ℃ for 24 hours to obtain a finished product.
Comparative example 2
A method for 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, to the first0.4g LiTFSI and 1.6g Al in a mixture 2 O 3 Obtaining a second mixed solution;
s3, coating the second mixed solution on a substrate, and drying at 80 ℃ for 24 hours to obtain a finished product.
Comparative example 3
A method of 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, 0.4g LiTFSI and 1.6g Al into the first mixed solution 2 O 3 Obtaining a second mixed solution;
s3, coating the second mixed solution on a substrate, and drying at 80 ℃ for 24 hours to obtain a finished product.
Comparative example 4
A method of 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 to the first mixed solution 4 And 1.6g Al 2 O 3 Obtaining a second mixed solution;
s3, coating the second mixed solution on a substrate, and drying at 80 ℃ for 24 hours to obtain a finished product.
The polymer electrolyte membranes produced in examples 1 to 6 and comparative examples 1 to 4 were subjected to heat shrinkage performance and ionic conductivity test, wherein the heat shrinkage performance test was carried out at a test temperature of 150℃for a test time of 1h.
The polymer electrolyte membranes prepared in examples 1 to 6 and comparative examples 1 to 4 were cut into wafers having a diameter of 100mm, placed in an oven at 150℃for 1 hour, taken out, and the diameter d of the wafer was measured again, and the heat shrinkage of the electrolyte membrane was calculated using formula 1.
Equation 1 is a thermal shrinkage rate calculation equation
The polymer electrolyte membranes prepared in examples 1 to 6 and comparative examples 1 to 4 were assembled into stainless steel sheet/electrolyte membrane/stainless steel sheet button cells, and electrochemical impedance spectra of the electrolyte membranes were measured using an ac impedance method using an electrochemical workstation. The thickness h and the diameter d of the polymer electrolyte sheet were measured with a thickness gauge, R is the polymer electrolyte membrane impedance, and the ion conductivity was calculated using formula 2.
σ＝h/(R·π(d/2)^2)
Equation 2 is an ionic conductivity calculation equation
The results of the tests are shown in FIG. 1, wherein the PPTA pulp content in the electrolyte slurries of examples 1-3 was 4%,10%,14.8% and the PPTA pulp content in the electrolyte slurries of examples 4-6 was 10%, respectively. The heat shrinkage of examples was smaller than that of comparative examples, and the heat shrinkage of example 2 was the smallest and the heat resistance was the best.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (7)
1. A method for preparing a solid polymer electrolyte membrane, comprising the steps of:
s1, dissolving a 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 uniformly dispersing to obtain polymer electrolyte slurry;
s4, coating the polymer electrolyte slurry on a substrate to obtain a polymer electrolyte wet film;
s5, drying the polymer electrolyte wet film to obtain a finished product;
the polymer electrolyte slurry comprises the following components in percentage by mass: 1-15% of a first polymer, 80-95% of an organic solvent, 1-10% of lithium salt and 1-15% of aromatic polyamide pulp;
in the step S3, the aromatic polyamide pulp is subjected to pretreatment, wherein the pretreatment comprises ultrasonic wave pre-impregnation and chemical modification;
the ultrasonic wave preimpregnation conditions are as follows: the ultrasonic treatment power is 500-800 w, and the treatment time is 5-15 min;
the chemical modification conditions are as follows: and (3) treating in 10% -15% sodium hydroxide solution for 2-4 hours.
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-paraphenylene terephthalamide pulp, poly-m-phenylene isophthalamide pulp and poly-p-benzamide pulp;
the specific surface area of the aromatic polyamide pulp is 1-12 m 2 /g。
3. The method for preparing 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, polymethyl methacrylate.
4. The method for producing a solid polymer electrolyte membrane according to claim 1, wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethane-sulfonyl imide, and lithium difluorooxalato-borate.
5. The method for producing a solid polymer electrolyte membrane according to 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 step S5, the drying temperature is 60 ℃ to 100 ℃ and the drying time is 5 to 25 hours.
7. A solid polymer electrolyte membrane produced by the method for producing a solid polymer electrolyte membrane according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111094481.3A CN114006032B (en) | 2021-09-17 | 2021-09-17 | Solid polymer electrolyte membrane and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111094481.3A CN114006032B (en) | 2021-09-17 | 2021-09-17 | Solid polymer electrolyte membrane and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114006032A CN114006032A (en) | 2022-02-01 |
| CN114006032B true CN114006032B (en) | 2024-01-26 |
Family
ID=79921452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111094481.3A Active CN114006032B (en) | 2021-09-17 | 2021-09-17 | Solid polymer electrolyte membrane and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114006032B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115602920A (en) * | 2022-11-04 | 2023-01-13 | 西安交通大学（Cn） | A kind of aramid fiber nanofiber reinforced ultra-thin polymer electrolyte membrane and preparation method thereof |
| CN116742107B (en) * | 2023-07-31 | 2024-03-26 | 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 |
| CN119650831B (en) * | 2024-10-22 | 2025-12-16 | 山东高登赛能源集团有限公司 | Polymer composite solid electrolyte membrane and its preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057470A (en) * | 1990-02-28 | 1992-01-01 | 纳幕尔杜邦公司 | Dispersible aramid pulp |
| JPH09302115A (en) * | 1996-05-14 | 1997-11-25 | Sumitomo Chem Co Ltd | Polymer electrolyte composite membrane and method for producing the same |
| CN107652494A (en) * | 2017-09-30 | 2018-02-02 | 青岛科技大学 | Rubber composite that a kind of Fanglun slurry cake strengthens with short basalt fiber orientation and preparation method thereof |
| CN110034330A (en) * | 2019-04-10 | 2019-07-19 | 华北电力大学 | A kind of preparation method of lithium/sode cell composite solid electrolyte |
| CN111816915A (en) * | 2020-06-10 | 2020-10-23 | 天津空间电源科技有限公司 | High-voltage polymer electrolyte and preparation method of solid-state battery thereof |
-
2021
- 2021-09-17 CN CN202111094481.3A patent/CN114006032B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057470A (en) * | 1990-02-28 | 1992-01-01 | 纳幕尔杜邦公司 | Dispersible aramid pulp |
| JPH09302115A (en) * | 1996-05-14 | 1997-11-25 | Sumitomo Chem Co Ltd | Polymer electrolyte composite membrane and method for producing the same |
| CN107652494A (en) * | 2017-09-30 | 2018-02-02 | 青岛科技大学 | Rubber composite that a kind of Fanglun slurry cake strengthens with short basalt fiber orientation and preparation method thereof |
| CN110034330A (en) * | 2019-04-10 | 2019-07-19 | 华北电力大学 | A kind of preparation method of lithium/sode cell composite solid electrolyte |
| CN111816915A (en) * | 2020-06-10 | 2020-10-23 | 天津空间电源科技有限公司 | High-voltage polymer electrolyte and preparation method of solid-state battery thereof |
Non-Patent Citations (1)
| Title |
|---|
| 芳纶浆粕预处理及在橡胶中的应用研究进展;丁佳伟等;合成橡胶工业;第43卷(第2期);正文第164页第1段、第165页第1-2段、第168页第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114006032A (en) | 2022-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114006032B (en) | Solid polymer electrolyte membrane and manufacturing method thereof | |
| US9136034B2 (en) | Polymer electrolyte membrane for a fuel cell, and method for preparing same | |
| CA2813564C (en) | Fluorine-based polymer electrolyte membrane | |
| KR101376362B1 (en) | Polymer Electrolyte Membrane for Fuel Cell and Method of manufacturing the same | |
| Zhang et al. | Water-soluble ammonium polyphosphate synchronously enables mechanically robust and flame-retardant cellulose composite separator for high safety lithium batteries | |
| CN107474270B (en) | Preparation method of polymer electrolyte membrane | |
| CN114400370B (en) | Fabric reinforced sulfide solid electrolyte, dry preparation method and application thereof | |
| CN115347322B (en) | Preparation method and application of porous polyolefin composite membrane | |
| Song et al. | Chitosan nanofiber paper used as separator for high performance and sustainable lithium-ion batteries | |
| CN119069956B (en) | A composite diaphragm for semi-solid lithium battery and its preparation method and application | |
| DE112017007529T5 (en) | Polymer electrolyte membrane, membrane electrode assembly and fuel cell with solid polymer electrolyte | |
| CN108807818B (en) | Aromatic polyamide composite diaphragm and preparation method thereof | |
| KR20190131690A (en) | Complex electrolyte membrane for PEMFC, manufacturing method thereof and membrane electrode assembly containing the same | |
| CN119381690A (en) | A cellulose-based lithium-ion battery separator capable of promoting lithium-ion migration, and a preparation method and application thereof | |
| CN113471531A (en) | Polymer solid electrolyte, preparation method thereof and solid battery | |
| JP2010170823A (en) | Complex type electrolyte membrane for fuel cell | |
| CN116544492A (en) | Composite electrolyte membrane and preparation method and application thereof | |
| Chen et al. | Polyimide/cellulose composite membrane with excellent heat-resistance and fast lithium-ion transport for lithium-ion batteries | |
| JP7807402B2 (en) | Ion-conductive membrane, component having ion-conductive membrane, and method of forming same | |
| KR101424850B1 (en) | Polyimide porous nanofiber web and Method for manufacturing the same | |
| Yuan et al. | Preparation of cellulose acetate based flexible separator and its application in zinc–air batteries | |
| Wang et al. | A biodegradable nano‐composite membrane for high‐safety and durable lithium‐ion batteries | |
| CN113488739B (en) | A three-layer porous membrane combined with electrospinning and phase separation method and its preparation method and application | |
| Cheng et al. | Aramid nanofibers/polydopamine coating polyethylene separator for lithium-ion battery | |
| CN119852643B (en) | Aramid diaphragm for lithium battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |