CN113882142B - Polyimide nanofiber membrane coated with cerium oxide nano layer on surface and preparation method thereof - Google Patents
Polyimide nanofiber membrane coated with cerium oxide nano layer on surface and preparation method thereof Download PDFInfo
- Publication number
- CN113882142B CN113882142B CN202111351799.5A CN202111351799A CN113882142B CN 113882142 B CN113882142 B CN 113882142B CN 202111351799 A CN202111351799 A CN 202111351799A CN 113882142 B CN113882142 B CN 113882142B
- Authority
- CN
- China
- Prior art keywords
- nanofiber membrane
- polyimide
- polyimide nanofiber
- cerium
- solution
- 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
- 239000002121 nanofiber Substances 0.000 title claims abstract description 156
- 239000012528 membrane Substances 0.000 title claims abstract description 152
- 239000004642 Polyimide Substances 0.000 title claims abstract description 133
- 229920001721 polyimide Polymers 0.000 title claims abstract description 133
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 44
- 239000002052 molecular layer Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 61
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 33
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 57
- 239000004952 Polyamide Substances 0.000 claims description 53
- 229920002647 polyamide Polymers 0.000 claims description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 claims description 2
- -1 cerium ions Chemical class 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000012643 polycondensation polymerization Methods 0.000 claims description 2
- 150000007519 polyprotic acids Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004176 ammonification Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 230000020477 pH reduction Effects 0.000 abstract description 2
- 239000000428 dust Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 50
- 239000000835 fiber Substances 0.000 description 49
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 40
- 238000009987 spinning Methods 0.000 description 35
- 239000002131 composite material Substances 0.000 description 25
- 238000003756 stirring Methods 0.000 description 20
- 229920005575 poly(amic acid) Polymers 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229960000583 acetic acid Drugs 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 239000012362 glacial acetic acid Substances 0.000 description 10
- 239000005457 ice water Substances 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- 239000012693 ceria precursor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/59—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
- D06M11/60—Ammonia as a gas or in solution
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Artificial Filaments (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention provides a polyimide nanofiber membrane coated with a cerium oxide nano layer on the surface and a preparation method thereof. Firstly preparing a polyimide nanofiber membrane by adopting an electrostatic spinning method, carrying out surface etching treatment by using an alkaline solution, preparing a polyimide nanofiber membrane with carboxylated surface after acidification, and then placing the polyimide nanofiber membrane in dilute ammonia water for ammonification; then placing the mixture in a cerium oxide precursor solution for reaction, then treating the mixture by hydrogen peroxide, and finally carrying out high-temperature heat treatment to obtain the polyimide nanofiber membrane with the surface coated with the cerium oxide nano layer. The coating of the cerium dioxide nano layer improves the mechanical property, thermal dimensional stability, wettability and high temperature resistance of the polyimide nano fiber membrane. The method has the advantages of simple operation process, easy flow, high production efficiency, full combination of the advantages of polyimide and an inorganic layer, and wide application prospect in the fields of lithium battery diaphragm, catalysis, filtration, flame retardance, dust removal and the like.
Description
Technical Field
The invention belongs to the technical field of polyimide nanofiber membranes, and relates to a preparation method of a polyimide nanofiber membrane with a cerium oxide nano layer coated on the surface and the polyimide nanofiber membrane with the cerium oxide nano layer coated on the surface.
Background
Since the advent of 1991, lithium ion batteries have been widely focused and widely used by people because of their high voltage, small size, high energy density, long cycle life, and rapid charge and discharge. The nobel chemical prize in 2019 awards scientists that have made outstanding contributions to the development of lithium ions, and the advent of lithium ion batteries has changed people's lifestyle. The battery separator enjoys the reputation of the battery "third electrode" and plays an important role in the production and use of the battery. This is because many characteristics such as charge/discharge performance, cycle performance, rate performance, and safety performance of the battery are determined by the performance of the separator, and whether the performance of the separator is good or bad plays an important role in improving the overall performance of the battery. The separator has the main function of separating the positive and negative poles of the battery to prevent the battery from being shorted by the contact of the two poles. In addition, the membrane can also act as a channel for ions. Polyolefin membranes have good mechanical properties and moderate porosity, but also have some problems due to their own structural features: (1) The non-polar nature makes its electrolyte wettability relatively poor, and the imbibition rate is lower, leads to the ionic conductivity of battery low, and the internal resistance is big to need wait for a long time after the electrolyte is poured into in the battery production process to the electrolyte infiltration diaphragm, has influenced the production efficiency of battery to a certain extent. (2) The softening temperature and the melting point (PP is 165 ℃ and PE is 135 ℃) of the polyolefin diaphragm are low, the battery can easily generate local high temperature in the high-power charge and discharge process, the diaphragm is molten and broken, internal short circuit occurs when the anode and the cathode are contacted, and finally the safety accident of the battery is induced. Therefore, development of a novel lithium ion battery diaphragm with high thermal stability and high electrolyte wettability is an urgent need in the field of lithium ion battery research.
The principle of the electrostatic spinning technology is as follows: electrostatically atomizing the polymer fluid to separate a fine polymer jet that can be run over long distances. During the movement, as the solvent evaporates, it eventually solidifies into a fiber. The droplets on the needle are transformed from spheres into cones under the action of an electric field, which cones are called "taylor cones", which extend from the needle tip into polymer fiber filaments [8,9] of nanoscale diameter, which after a period of time form a nanofiber membrane of a certain thickness. The fiber morphology is comprehensively influenced by solution evaporation rate, polymer concentration, spinning distance, accelerating voltage and the like, and compared with other manufacturing processes, the thickness and the diameter of the electrostatic spinning film are smaller and more controllable. At present, the electrostatic spinning process can be used for preparing nanofiber materials with various morphologies such as coaxial fibers, hollow fibers, porous fibers and the like, and has wide application prospects in industries such as filtration, medical treatment, catalysis, energy sources and the like.
Polyimide (PI for short) is a high-performance polymer, and its main chain contains imide ring, so that it has excellent high-low temperature resistance, excellent mechanical property, good chemical stability, excellent dielectric and irradiation resistance, and is one of organic high-molecular materials with optimum comprehensive properties, so that it is called as "energy hand for solving problems", and can be extensively used in the fields of aviation, aerospace, microelectronics and advanced composite material, etc.. Polyimide can be classified into aliphatic PI and aromatic PI according to the difference of main chain structures, and the aromatic PI main chain contains benzene ring structures, so that the comprehensive performance of the polyimide is far better than that of aliphatic polyimide, and the polyimide becomes a high-performance polymer with the highest application degree at present. The polyimide nanofiber membrane prepared by the electrostatic spinning method has the properties of high porosity, flexibility and the like besides the properties of polyimide, so that the polyimide nanofiber membrane becomes one of the optimal choices of a new generation of high-temperature-resistant and high-safety lithium ion battery separator. The polyimide nanofiber surface is coated with a layer of inorganic ceramic, so that the temperature resistance, flame retardance, wettability and strength of the polyimide nanofiber membrane can be further improved, the defect that the inorganic ceramic lacks flexibility is overcome, and the preparation of the polyimide fiber flexible membrane coated with the inorganic ceramic is realized. Cerium oxide is used as a novel ceramic material and has outstanding high temperature resistance, infiltration performance and flame retardance. The invention adopts the organic polymer material polyimide fiber as a matrix and combines the inorganic material cerium dioxide to prepare the cerium dioxide coated polyimide composite nanofiber membrane, establishes a novel method and realizes the controllable coating of the cerium dioxide inorganic ceramic layer on the polyimide nanofiber. The composite nanofiber membrane has excellent high temperature resistance, flame retardance, wettability, flexibility and excellent strength and porosity, and can be used as a novel lithium ion battery diaphragm material.
Disclosure of Invention
The invention provides a polyimide nanofiber membrane coated with a cerium dioxide nano layer on the surface and a preparation method thereof, and the cerium dioxide coated polyimide composite nanofiber membrane has excellent heat resistance, high porosity, chemical stability, thermal dimensional stability, mechanical property and wettability.
The polyimide nanofiber membrane with the surface coated with the ceria nanofiber layer, which is also called as a polyimide/ceria composite nanofiber membrane, is provided with the ceria layer on the surface of the polyimide nanofiber membrane, wherein the thickness of the polyimide nanofiber membrane is 5-60 mu m, the diameter of fibers in the polyimide nanofiber membrane is 10-600nm, and the thickness of the ceria layer is 2-300nm.
Further, the polyimide nanofiber membrane coated with the ceria nanolayer has a porosity of 70% -95%, preferably 80% -92%.
Further, the thickness of the polyimide nanofiber membrane is preferably 15-20 μm.
Further, the diameter of the fibers in the polyimide nanofiber membrane is preferably 20-700nm, and the thickness of the cerium oxide layer is preferably 5-100nm.
The preparation method of the polyimide nanofiber membrane with the surface coated with the cerium oxide nano layer comprises the following steps:
a: dissolving cerium salt in water to obtain a precursor solution of cerium oxide with the concentration of 0.01-3 mol/L;
b: preparing polyamide acid solution with the concentration of 3-25 wt% by solution condensation polymerization of polybasic acid anhydride and polybasic amine, preparing polyamide acid nanofiber membrane by using electrostatic spinning method, and performing heat treatment on the polyamide acid nanofiber membrane to obtain a completely imidized polyimide nanofiber membrane;
c: placing the polyimide nanofiber membrane in an alkaline solution for a certain time to hydrolyze and open the surface of the polyimide nanofiber membrane, then acidizing the polyimide nanofiber membrane in a dilute acid solution to obtain a polyimide nanofiber membrane with carboxylated surface, and then placing the polyimide nanofiber membrane in a dilute ammonia water solution with a certain concentration for treatment to obtain a polyimide nanofiber membrane with aminated surface;
d: placing the polyimide nanofiber membrane obtained by treatment in the step C in the precursor solution of cerium dioxide in the step A for reacting for a certain time, taking out, washing with deionized water, placing in a hydrogen peroxide solution, and reacting for 1-3h;
e: and D, carrying out gradient heating heat treatment on the nanofiber membrane obtained in the step D to obtain the polyimide nanofiber membrane with the surface coated with the cerium oxide nano layer.
Further, the cerium salt in the step A is cerium nitrate, cerium chloride, ammonium cerium nitrate and cerium carbonate, and the concentration of cerium ions in the precursor solution of cerium oxide is preferably 0.05 to 2.5mol/L, particularly preferably 0.1 to 2mol/L.
Further, the electrospinning in step B is a special fiber manufacturing process, and the polymer solution or melt is subjected to jet spinning in a strong electric field. Under the action of an electric field, the liquid drop at the needle is changed from a ball shape into a conical shape (namely, a Taylor cone) and extends from the tip of the cone to obtain fiber filaments, and the polymer filaments with the nanometer diameters can be produced. The invention takes the polyamic acid solution as electrostatic spinning solution, prepares the polyamic acid solution into nano fiber through electrostatic spinning, in the process, besides the influence of spinning concentration on the nanofiber, the necessary spinning parameter is one of reasons for whether the electrostatic spinning is successful, and the method takes needle spinning as an example, has the voltage of 20-30KV and the propelling quantity of 0.3-0.7 mL/h, and selects an 18-gauge needle head, and the speed of a receiving roller is 300-600rpm.
Further, the alkaline solution in the step C is one or a mixture of sodium hydroxide, potassium hydroxide and lithium hydroxide, and the concentration of the alkaline solution is 0.5-2mol/L; the dilute acid solution is any one of acetic acid, trifluoroacetic acid, formic acid, hydrochloric acid and sulfuric acid, and the pH value is adjusted to be 5-6; the pH value of the dilute ammonia water is adjusted to 9-13.
Further, in the step D, the treatment time of the polyamic acid nanofiber membrane in the precursor solution of cerium oxide is 1min to 3h, preferably 2min to 2h, particularly preferably 10min to 1h; the hydrogen peroxide is added at a concentration of 1% to 20%, preferably 2% to 15%, particularly preferably 3% to 10%; the reaction time is 0.5-30min, preferably 1-25min.
Further, the heat treatment time in the step E is 0.1-5h, preferably 1-4h, and the heat treatment condition is that the temperature is raised from room temperature to 250-400 ℃, preferably 300-350 ℃, and the heating rate is 1-20 ℃/min, preferably 2-10 ℃/min.
Compared with the prior art, the invention has the following excellent effects:
1. the invention establishes a new method, takes polyimide nano fiber as a matrix, utilizes a new thought of ammonification after surface alkaline hydrolysis acidification, and directly treats the polyimide nano fiber membrane by hydrogen peroxide after the cerium oxide precursor ions are combined, namely, the preparation of the composite nano fiber membrane coated with the cerium oxide inorganic ceramic layer is realized in one step, the process step of adding ammonia water for post treatment in the final process of generating the traditional cerium oxide is omitted, the steps are simpler, and the controllability is strong.
2. The polyimide coaxial cladding cerium dioxide nanofiber membrane prepared by the invention has the advantages of excellent high temperature resistance (capable of bearing high temperature of 500 ℃), thermal dimensional stability (shrinkage rate of 0 at 310 ℃), wettability (contact angle with electrolyte is about 13 ℃), flame retardance and the like, and high porosity (up to 92%), high strength (up to 50 MPa) and the like, combines the dimensional performance of polyimide and the flame retardance and wettability of cerium dioxide ceramic, has the potential of being used as a novel high-performance lithium battery diaphragm, and is a novel organic-inorganic composite material.
3. By utilizing the characteristic that active groups contained on the PI surface of the surface alkaline hydrolysis ring-opening can complex cations, the polyimide nanofiber membrane coaxially coated with inorganic ceramics can be prepared, and compared with a multilayer diaphragm prepared by a coating method, the nanofiber membrane has a more uniform fiber structure, lighter weight and better electrolyte wettability.
4. The process equipment requirements of the polyimide coaxial coated cerium dioxide nanofiber membrane are easy to meet, the process is simple, the operation is simple and convenient, the repeatability is high, and the controllable preparation of nanofiber membranes with different nanofiber diameters and different thicknesses and the controllable coating of cerium dioxide on the surface of the nanofiber membrane can be realized through the adjustment of process parameters.
Drawings
FIG. 1 is a scanning electron microscope image of a polyimide/ceria composite nanofiber membrane prepared according to example 1, with a magnification of 30000 times on the left and 1000 times on the right;
FIG. 2 is a scanning electron microscope image of a polyimide/ceria composite nanofiber membrane prepared according to example 2, with magnification of 20000 times on the left and 1000 times on the right;
FIG. 3 is a scanning electron microscope image of a polyimide/ceria composite nanofiber membrane prepared according to example 3, with magnification of 20000 times on the left and 1000 times on the right;
FIG. 4 is a scanning electron microscope image of a polyimide/ceria composite nanofiber membrane prepared according to example 4, with magnification of 20000 times on the left and 2000 times on the right.
FIG. 5 is a scanning electron microscope image of a polyimide/ceria composite nanofiber membrane prepared according to example 5, with a magnification of 30000 times on the left and 2000 times on the right.
FIG. 6 is a scanning electron microscope image of the polyimide nanofiber membrane prepared in example 1, with magnification of 50000 times on the left and 2000 times on the right.
FIG. 7 is a scanning electron microscope image of ash obtained by calcining the polyimide/ceria composite nanofiber membrane prepared in example 1 at a high temperature of 900℃for 1.5 hours, with a magnification of 30000 times on the left and 2000 times on the right.
Detailed Description
The invention is further illustrated below in conjunction with specific embodiments. It should be noted that: the following examples are only for illustrating the invention and are not intended to limit the technical solutions described in the invention. Thus, although the present invention has been described in detail with reference to the following examples, it will be understood by those skilled in the art that the present invention may be modified or equivalents; all technical solutions and modifications thereof that do not depart from the spirit and scope of the present invention are intended to be included in the scope of the appended claims.
Example 1
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, performing thermal imidization to obtain the polyimide nanofiber membrane, firstly placing the polyimide nanofiber membrane in 0.1mol/L potassium hydroxide solution for etching, adding 7ml of glacial acetic acid, dropwise adding 10 drops of diluted ammonia water, then placing the polyimide nanofiber membrane in 1mol/L cerium oxide precursor solution, adding 5ml of hydrogen peroxide solution, and finally performing thermal treatment to obtain the polyimide/cerium oxide composite nanofiber membrane. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 300℃at a heating rate of 2℃per minute, and maintained for 2 hours, thereby obtaining a polyimide nanofiber film. (2) 20ml deionized water and 25ml absolute ethanol were measured and mixed well in a beaker. 14.68g of cerium nitrate was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved, thereby obtaining a precursor solution of cerium oxide. (3) And placing the polyimide nanofiber membrane into a 0.1mol/L potassium hydroxide solution for etching for 1min. (4) 5ml of glacial acetic acid was added to adjust the pH to 5, then 10 drops of dilute ammonia were added to adjust the pH to 9, and the mixture was placed in a 1mol/L ceria precursor solution for 1h. (5) A further amount of 7.87ml of H was added 2 O 2 Fully reacting for 20min, taking out and airing. (5) And (3) placing the nanofiber membrane obtained in the previous step in a baking oven at 400 ℃ for heat preservation for 2 hours to obtain the polyimide nanofiber membrane with the surface coated with cerium oxide, wherein the morphology of the obtained fiber is shown in figure 1. Example 1 preparationThe shrinkage rate of the polyimide/ceria composite nanofiber membrane is 0 after heat preservation for 1h at 400 ℃, and the tensile strength is 35.9MPa.
Comparative example 1
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, and obtaining the polyimide nanofiber membrane after thermal imidization. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 350℃at a heating rate of 4℃per minute, and maintained for 1 hour, thereby obtaining a polyimide nanofiber film. The polyimide nanofiber membrane prepared in comparative example 1 had a shrinkage of 0.3% and a tensile strength of 13.3MPa when it was heat-preserved at 400 ℃ for 1 hour.
Example 2
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, performing thermal imidization to obtain the polyimide nanofiber membrane, firstly placing the polyimide nanofiber membrane in 0.1mol/L potassium hydroxide solution for etching, adding 7ml of glacial acetic acid, dropwise adding 10 drops of diluted ammonia water, then placing the polyimide nanofiber membrane in 1mol/L cerium oxide precursor solution, adding 5ml of hydrogen peroxide solution, and finally performing thermal treatment to obtain the polyimide/cerium oxide composite nanofiber membrane. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and applying electrostatic spinningThe polyamide acid fiber membrane is prepared by the technology, and the specific parameters of an electrostatic spinning machine are spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 300℃at a heating rate of 2℃per minute, and maintained for 2 hours, thereby obtaining a polyimide nanofiber film. (2) 20ml deionized water and 25ml absolute ethanol were measured and mixed well in a beaker. 14.68g of cerium nitrate was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved, thereby obtaining a precursor solution of cerium oxide. (3) The polyimide nanofiber membrane was placed in a 0.1mol/L potassium hydroxide solution and etched for 30s. (4) 5ml of glacial acetic acid was added to adjust the pH to 5, then 10 drops of dilute ammonia were added to adjust the pH to 9, and the mixture was placed in a 1mol/L ceria precursor solution for 1h. (5) A further amount of 7.87ml of H was added 2 O 2 Fully reacting for 20min, taking out and airing. (5) And (3) placing the nanofiber membrane obtained in the previous step in a baking oven at 400 ℃ for heat preservation for 2 hours to obtain the polyimide nanofiber membrane with the surface coated with cerium oxide, wherein the morphology of the obtained fiber is shown in figure 2. The polyimide/ceria composite nanofiber membrane prepared in example 2 has a shrinkage of 0 and a tensile strength of 33.6MPa when it is heat-preserved at 400 ℃ for 1 hour.
Comparative example 2
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, and obtaining the polyimide nanofiber membrane after thermal imidization. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 350℃at a heating rate of 4℃per minute, and maintained for 1 hour, thereby obtaining a polyimide nanofiber film. The polyimide nanofiber membrane prepared in comparative example 2 had a shrinkage of 0.3% and a tensile strength of 13.3MPa when it was heat-preserved at 400 ℃ for 1 hour.
Example 3
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, performing thermal imidization to obtain the polyimide nanofiber membrane, firstly placing the polyimide nanofiber membrane in 0.1mol/L potassium hydroxide solution for etching, adding 7ml of glacial acetic acid, dropwise adding 10 drops of diluted ammonia water, then placing the polyimide nanofiber membrane in 1mol/L cerium oxide precursor solution, adding 5ml of hydrogen peroxide solution, and finally performing thermal treatment to obtain the polyimide/cerium oxide composite nanofiber membrane. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 300℃at a heating rate of 2℃per minute, and maintained for 2 hours, thereby obtaining a polyimide nanofiber film. (2) 20ml deionized water and 25ml absolute ethanol were measured and mixed well in a beaker. 14.68g of cerium nitrate was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved, thereby obtaining a precursor solution of cerium oxide. (3) The polyimide nanofiber membrane was etched in 0.1mol/L potassium hydroxide solution for 10s. (4) 5ml of glacial acetic acid was added to adjust the pH to 5, then 10 drops of dilute ammonia were added to adjust the pH to 9, and the mixture was placed in a 1mol/L ceria precursor solution for 1h. (5) And then7.87ml of H was added 2 O 2 Fully reacting for 20min, taking out and airing. (5) And (3) placing the nanofiber membrane obtained in the previous step in a baking oven at 400 ℃ for heat preservation for 2 hours to obtain the polyimide nanofiber membrane with the surface coated with cerium oxide, wherein the morphology of the obtained fiber is shown in figure 3. The polyimide/ceria composite nanofiber membrane prepared in example 3 has a shrinkage of 0 and a tensile strength of 30.9MPa when it is heat-preserved at 400 ℃ for 1 hour.
Comparative example 3
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, and obtaining the polyimide nanofiber membrane after thermal imidization. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 350℃at a heating rate of 4℃per minute, and maintained for 1 hour, thereby obtaining a polyimide nanofiber film. The polyimide nanofiber membrane prepared in comparative example 3 had a shrinkage of 0.3% and a tensile strength of 13.3MPa when it was heat-preserved at 400 ℃ for 1 hour.
Example 4
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, performing thermal imidization to obtain the polyimide nanofiber membrane, firstly placing the polyimide nanofiber membrane in a 1mol/L potassium hydroxide solution for etching, adding 7ml of glacial acetic acid, dropwise adding 10 drops of diluted ammonia water, then placing the polyimide nanofiber membrane in a 1mol/L cerium oxide precursor solution, adding 5ml of hydrogen peroxide solution, and finally performing thermal treatment to obtain the polyimide/cerium oxide composite nanofiber membrane. (1) 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1 are weighed out, and the ODA is fully reactedPartially dissolving in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, after ODA is completely dissolved in DMF, under the condition of ice-water bath, adding PMDA step by step to obtain polyamic acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamic acid solution into a 20ml syringe, and preparing the polyamic acid fiber membrane by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 300℃at a heating rate of 2℃per minute, and maintained for 2 hours, thereby obtaining a polyimide nanofiber film. (2) 20ml deionized water and 25ml absolute ethanol were measured and mixed well in a beaker. 14.68g of cerium nitrate was weighed, added to a mixed solvent of ethanol and deionized water, and stirred to be sufficiently dissolved, thereby obtaining a precursor solution of cerium oxide. (3) And placing the polyimide nanofiber membrane into 0.1mol/L potassium hydroxide solution to etch for 10s. (4) 5ml of glacial acetic acid was added to adjust the pH to 5, then 10 drops of dilute ammonia were added to adjust the pH to 9, and the mixture was placed in a 1mol/L precursor solution of cerium oxide for 1h. (5) A further amount of 7.87ml of H was added 2 O 2 Fully reacting for 20min, taking out and airing. (5) And (3) placing the nanofiber membrane obtained in the previous step in a baking oven at 400 ℃ for heat preservation for 2 hours to obtain the polyimide nanofiber membrane with the surface coated with cerium oxide, wherein the morphology of the obtained fiber is shown in figure 4. The polyimide/ceria composite nanofiber membrane prepared in example 4 has a shrinkage of 0 and a tensile strength of 30.6MPa when it is heat-preserved at 400 ℃ for 1 hour.
Comparative example 4
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, and obtaining the polyimide nanofiber membrane after thermal imidization. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 350℃at a heating rate of 4℃per minute, and maintained for 1 hour, thereby obtaining a polyimide nanofiber film. The polyimide nanofiber membrane prepared in comparative example 1 had a shrinkage of 0.3% and a tensile strength of 13.3MPa when it was heat-preserved at 400 ℃ for 1 hour.
Example 5
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, performing thermal imidization to obtain the polyimide nanofiber membrane, firstly placing the polyimide nanofiber membrane in 0.5mol/L potassium hydroxide solution for etching, adding 7ml of glacial acetic acid, dropwise adding 10 drops of diluted ammonia water, then placing the polyimide nanofiber membrane in 1mol/L cerium oxide precursor solution, adding 5ml of hydrogen peroxide solution, and finally performing thermal treatment to obtain the polyimide/cerium oxide composite nanofiber membrane. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 300℃at a heating rate of 2℃per minute, and maintained for 2 hours, thereby obtaining a polyimide nanofiber film. (2) 20ml deionized water and 25ml absolute ethanol were measured and mixed well in a beaker. 14.68g of cerium nitrate is weighed and added into a mixed solvent of ethanol and deionized water, and stirred to be fully dissolvedA precursor solution of ceria was obtained. (3) The polyimide nanofiber membrane was etched in 0.1mol/L potassium hydroxide solution for 10s. (4) 5ml of glacial acetic acid was added to adjust the pH to 5, then 10 drops of dilute ammonia were added to adjust the pH to 9, and the mixture was placed in a 1mol/L ceria precursor solution for 1h. (5) A further amount of 7.87ml of H was added 2 O 2 Fully reacting for 20min, taking out and airing. (5) And (3) placing the nanofiber membrane obtained in the previous step in a baking oven at 400 ℃ for heat preservation for 2 hours to obtain the polyimide nanofiber membrane with the surface coated with cerium oxide, wherein the morphology of the obtained fiber is shown in figure 5. The polyimide/ceria composite nanofiber membrane prepared in example 5 has a shrinkage of 0 and a tensile strength of 33.9MPa when it is heat-preserved at 400 ℃ for 1 hour.
Comparative example 5
Preparing a polyamide acid nanofiber membrane of a PMDA/ODA system, and obtaining the polyimide nanofiber membrane after thermal imidization. (1) Weighing 2.0g of pyromellitic dianhydride (PMDA) and 1.8g of 4,4' -diaminodiphenyl ether (ODA) in a molar ratio of 1:1, dissolving the ODA in 30ml of N, N-Dimethylformamide (DMF) solvent, mechanically stirring, adding the PMDA step by step under the condition of ice-water bath after the ODA is completely dissolved in the DMF to obtain a polyamide acid solution with moderate viscosity, mechanically stirring for 2h, filling the polyamide acid solution into a 20ml syringe, and preparing the polyamide acid fiber film by using an electrostatic spinning technology, wherein the specific parameters of an electrostatic spinning machine are as spinning voltage: 29kV; spinning temperature: room temperature; spinning humidity: 30%; syringe needle diameter: number 18; receiving roller rotation speed: 500rpm; reception distance: 20cm. Placing the prepared polyamide acid fiber membrane in an ultra-clean bench for 12 hours; the obtained polyamic acid fiber film was placed in a heat furnace, gradually heated to 350℃at a heating rate of 4℃per minute, and maintained for 1 hour, thereby obtaining a polyimide nanofiber film. The polyimide nanofiber membrane prepared in comparative example 1 had a shrinkage of 0.3% and a tensile strength of 13.3MPa when it was heat-preserved at 400 ℃ for 1 hour.
Experimental tests show that by comparing the pure polyimide nanofiber membrane with the scanning electron microscope images of the ceria coated polyimide composite nanofiber membranes shown in fig. 6, the fiber surface of the pure polyimide nanofiber membrane can be clearly seen to be smooth, and the rough surface coating structure can be observed on the composite nanofiber surface, namely, the ceria nano layer is tightly coated on the polyimide fiber surface. FIG. 7 is a scanning electron microscope image of ash obtained by calcining the ceria-coated polyimide composite nanofiber membrane prepared in example 1 at 900℃for 1.5 hours. The existence of cerium oxide is proved by observing that substances remain after high-temperature calcination at 900 ℃ and the appearance of the fibers, and the phenomena of figures 1-7 show that the polyimide/cerium oxide composite nanofiber membrane has been successfully prepared.
Claims (6)
1. The preparation method of the polyimide nanofiber membrane with the surface coated with the cerium oxide nano layer is characterized by comprising the following steps of:
a: dissolving cerium salt in water to obtain a precursor solution of cerium oxide with the concentration of 0.01-3 mol/L;
b: preparing polyamide acid solution with the concentration of 3-25 wt% by solution condensation polymerization of polybasic acid anhydride and polybasic amine, preparing polyamide acid nanofiber membrane by using electrostatic spinning method, and performing heat treatment on the polyamide acid nanofiber membrane to obtain a completely imidized polyimide nanofiber membrane;
c: placing the polyimide nanofiber membrane obtained in the step B in an alkaline solution to hydrolyze and open the surface of the polyimide nanofiber membrane, then acidizing the polyimide nanofiber membrane in a dilute acid solution to obtain a polyimide nanofiber membrane with carboxylated surface, and then placing the polyimide nanofiber membrane in a dilute ammonia water solution to treat the polyimide nanofiber membrane to obtain a polyimide nanofiber membrane with aminated surface;
d: placing the polyimide nanofiber membrane obtained by treatment in the step C into the precursor solution of cerium dioxide in the step A for reaction, taking out, washing with deionized water, placing into hydrogen peroxide solution, and reacting for 1-3h;
e: and D, carrying out heating heat treatment on the nanofiber membrane obtained in the step D to obtain the polyimide nanofiber membrane with the surface coated with the cerium oxide nano layer.
2. The preparation method according to claim 1, wherein the cerium salt in the step A is cerium nitrate, cerium chloride, ammonium cerium nitrate or cerium carbonate, and the concentration of cerium ions in the precursor solution of cerium oxide is 0.05-2.5 mol/L.
3. The preparation method according to claim 1, wherein the alkaline solution in the step C is one or a mixture of sodium hydroxide, potassium hydroxide and lithium hydroxide, the concentration of the alkaline solution is 0.5-2mol/L, the dilute acid solution is any one of acetic acid, trifluoroacetic acid, formic acid, hydrochloric acid and sulfuric acid, and the pH value is adjusted to 5-6; the pH value of the dilute ammonia water is adjusted to 9-13.
4. The method according to claim 1, wherein in the step D, the treatment time of the polyimide nanofiber membrane in the precursor solution of ceria is 1min to 3h; the concentration of the added hydrogen peroxide is 1% -20%; the reaction time is 0.5-30min.
5. The preparation method according to claim 1, wherein the heat treatment time in the step E is 0.1-5h, the heat treatment condition is that the temperature is raised from room temperature to 250-400 ℃, and the heating rate is 1-20 ℃/min.
6. A polyimide nanofiber membrane coated with a cerium oxide nanolayer prepared according to any one of the preparation methods of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111351799.5A CN113882142B (en) | 2021-11-16 | 2021-11-16 | Polyimide nanofiber membrane coated with cerium oxide nano layer on surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111351799.5A CN113882142B (en) | 2021-11-16 | 2021-11-16 | Polyimide nanofiber membrane coated with cerium oxide nano layer on surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113882142A CN113882142A (en) | 2022-01-04 |
| CN113882142B true CN113882142B (en) | 2024-02-02 |
Family
ID=79018121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111351799.5A Active CN113882142B (en) | 2021-11-16 | 2021-11-16 | Polyimide nanofiber membrane coated with cerium oxide nano layer on surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113882142B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105970485A (en) * | 2016-06-06 | 2016-09-28 | 北京化工大学常州先进材料研究院 | Polyimide-zirconium dioxide composite nanofiber membrane and preparation method thereof |
| CN108855236A (en) * | 2018-07-17 | 2018-11-23 | 成都市水泷头化工科技有限公司 | A kind of recyclable high temperature resistant photocatalysis film and preparation method for sewage treatment |
| CN111394892A (en) * | 2020-03-26 | 2020-07-10 | 北京化工大学常州先进材料研究院 | Polyimide nanofiber membrane coaxially coated with nano zirconium dioxide inorganic layer and preparation method thereof |
| CN112510320A (en) * | 2020-11-18 | 2021-03-16 | 东莞市魔方新能源科技有限公司 | Preparation method of diaphragm for lithium ion battery, diaphragm and lithium ion battery |
| CN113622089A (en) * | 2021-09-08 | 2021-11-09 | 北京化工大学常州先进材料研究院 | Polyimide/cerium dioxide composite nanofiber membrane and preparation method thereof |
-
2021
- 2021-11-16 CN CN202111351799.5A patent/CN113882142B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105970485A (en) * | 2016-06-06 | 2016-09-28 | 北京化工大学常州先进材料研究院 | Polyimide-zirconium dioxide composite nanofiber membrane and preparation method thereof |
| CN108855236A (en) * | 2018-07-17 | 2018-11-23 | 成都市水泷头化工科技有限公司 | A kind of recyclable high temperature resistant photocatalysis film and preparation method for sewage treatment |
| CN111394892A (en) * | 2020-03-26 | 2020-07-10 | 北京化工大学常州先进材料研究院 | Polyimide nanofiber membrane coaxially coated with nano zirconium dioxide inorganic layer and preparation method thereof |
| CN112510320A (en) * | 2020-11-18 | 2021-03-16 | 东莞市魔方新能源科技有限公司 | Preparation method of diaphragm for lithium ion battery, diaphragm and lithium ion battery |
| CN113622089A (en) * | 2021-09-08 | 2021-11-09 | 北京化工大学常州先进材料研究院 | Polyimide/cerium dioxide composite nanofiber membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高分子涂层制备技术研究进展;李建昌;李宏宇;林小星;陈建;杨贻谋;;真空(04);第6-14页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113882142A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111394892B (en) | Polyimide nanofiber membrane coaxially coated with nano zirconium dioxide inorganic layer and preparation method thereof | |
| CN108914550B (en) | Preparation method of polyimide fiber membrane with surface coated with zirconium dioxide nano layer | |
| WO2011025259A2 (en) | Polymer electrolyte membrane for a fuel cell, and method for preparing same | |
| CN108774808B (en) | Polyimide nanofiber membrane with cross-linked appearance and zirconium dioxide coated surface and preparation method thereof | |
| CN113493959B (en) | Polyimide nanofiber membrane with surface coated with silicon dioxide | |
| CN113622089B (en) | Polyimide/cerium dioxide composite nanofiber membrane and preparation method thereof | |
| JP2013536323A (en) | POLYIMIDE POROUS WEB, PROCESS FOR PRODUCING THE SAME, AND ELECTROLYTE MEMBRANE CONTAINING THE SAME | |
| CN113969006B (en) | Polyimide-coated modified polyolefin composite diaphragm and preparation method thereof | |
| CN109860485B (en) | Polyimide nanofiber diaphragm and manufacturing method thereof | |
| CN111155239A (en) | Preparation method of electrostatic spinning polyimide/MXene electromagnetic shielding film | |
| CN112216928A (en) | Modified composite heat-resistant lithium ion battery diaphragm and preparation method thereof | |
| CN113638239B (en) | Polyimide/silver composite film with electromagnetic shielding function and preparation method thereof | |
| CN108755104B (en) | Preparation method of surface-modified titanium dioxide nanoparticle polyimide fibrous membrane | |
| CN109853135B (en) | Polybenzimidazole coated polyimide nanofiber core-shell structure nanofiber membrane and preparation method thereof | |
| CN113882142B (en) | Polyimide nanofiber membrane coated with cerium oxide nano layer on surface and preparation method thereof | |
| CN113897775A (en) | Cerium dioxide coated polyimide composite nanofiber membrane and preparation method thereof | |
| CN113529404B (en) | Polyimide nanofiber membrane with surface uniformly coated with controllable nano zirconium dioxide inorganic layer and preparation method thereof | |
| CN115896863B (en) | Composite diaphragm for ultrathin alkaline water electrolysis, preparation method thereof and alkaline water electrolysis device | |
| KR101424850B1 (en) | Polyimide porous nanofiber web and Method for manufacturing the same | |
| CN113725554A (en) | Polyimide/magnesium oxide composite lithium ion battery diaphragm and preparation method thereof | |
| CN113956658B (en) | Polyimide/titanium dioxide composite microsphere and preparation method thereof | |
| CN116315435A (en) | Fiber diaphragm for lithium battery and preparation method thereof | |
| CN113690457B (en) | Spinning solution for fuel cell and preparation method of carbon paper of spinning solution | |
| CN111455476B (en) | Polyimide nanofiber membrane coaxially coated with aluminum oxide and preparation method thereof | |
| CN113494020B (en) | Method for coating surface of polyimide nanofiber membrane with boehmite ceramic layer |
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 |