CN110144674B - Preparation method of flexible conductive ceramic fiber membrane - Google Patents
Preparation method of flexible conductive ceramic fiber membrane Download PDFInfo
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- CN110144674B CN110144674B CN201910501147.1A CN201910501147A CN110144674B CN 110144674 B CN110144674 B CN 110144674B CN 201910501147 A CN201910501147 A CN 201910501147A CN 110144674 B CN110144674 B CN 110144674B
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- 239000000835 fiber Substances 0.000 title claims abstract description 142
- 239000012528 membrane Substances 0.000 title claims abstract description 123
- 239000000919 ceramic Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000002243 precursor Substances 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 43
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000002121 nanofiber Substances 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 238000009987 spinning Methods 0.000 claims description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical group O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011224 oxide ceramic Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- ADVORQMAWLEPOI-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxotitanium Chemical compound [Ti]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O ADVORQMAWLEPOI-XHTSQIMGSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 230000009467 reduction Effects 0.000 description 12
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229940120638 avastin Drugs 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- 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
- D04H1/413—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 containing granules other than absorbent substances
-
- 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
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- 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
- D06M11/83—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 metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
Abstract
The invention provides a preparation method of a flexible conductive titanium dioxide ceramic fiber membrane, which is characterized by comprising the following steps: step 1: preparing TiO2A precursor solution, wherein the precursor solution contains a titanium source, a high molecular polymer and a solvent; step 2: the obtained TiO is mixed2Performing electrostatic spinning on the precursor solution to obtain a precursor nanofiber membrane; and step 3: calcining the obtained precursor nanofiber membrane in air atmosphere to obtain flexible TiO2A ceramic fiber membrane; and 4, step 4: the obtained flexible TiO is mixed2And (3) contacting the ceramic fiber membrane with a metal lithium sheet in a vacuum atmosphere, and dropwise adding a solvent on the surface of the fiber membrane to obtain the flexible conductive titanium dioxide ceramic fiber membrane.
Description
Technical Field
The invention relates to a preparation method of a flexible ceramic fiber membrane and a method for rapidly improving the conductivity of the flexible ceramic fiber membrane at normal temperature, belonging to the technical field of new material processing.
Background
Due to the unique electronic structure, excellent thermal property and chemical stability, the oxide ceramic is widely researched and applied in the fields of energy storage, photocatalysis, sensing and the like. However, these materials typically have a larger bandgap and lower room temperature carrier mobility, resulting in lower electrical conductivity. These factors severely limit the range of applications for oxide ceramic materials. Therefore, the finding of the oxide ceramic material with excellent conductivity is significant.
Among the numerous oxide ceramic materials, TiO2Has attracted extensive attention due to its advantages of abundance, cheapness, no toxicity, unique optical and electrical properties, etc. However, TiO2Ceramics have low electrical conductivity and are almost insulators. Research shows that the black TiO2The nanometer material can greatly promote TiO2The conductivity of the composite material is further expanded, and the application range of the composite material is expanded, wherein the composite material comprises the fields of high-performance photocatalysis, lithium ion batteries, super capacitors, fuel cells, photoelectrochemical sensors, field emission electrodes, microwave absorbers and the like. At present, researchers have developed many methods for preparing black TiO2Involving the use of H at elevated temperatures2Or N2Reduction of TiO2Heating TiO with metallic Al or Mg powder2Reducing the particles, and applying plasma treatment. Chen (Science,2011,331(6018):746-750) et al treat TiO by hydrogen at 200 deg.C2The nano-particle electrode material lasts for 5 days to obtain black TiO2The light energy conversion efficiency of the nano-particles is remarkably improved. Wang (Energy)&Environmental Science,2013,6(10):3007-2And (3) nano materials. However, these reduction methods have some problems. For example, high energy particle reduction of TiO2Expensive equipment support is required; the reduction of hydrogen and metal needs to be carried out for a long time at high temperature, so that the preparation cost is greatly improved.
Disclosure of Invention
The invention aims to provide a preparation method of a flexible conductive ceramic fiber membrane with low cost.
In order to achieve the above object, the present invention provides a method for preparing a flexible conductive titanium dioxide ceramic fiber membrane, comprising:
step 1: preparing TiO2A precursor solution, wherein the precursor solution contains a titanium source, a high molecular polymer and a solvent;
step 2: the obtained TiO is mixed2Performing electrostatic spinning on the precursor solution to obtain a precursor nanofiber membrane, applying a constant-temperature thermal field of 25-55 ℃ in a spinning interval during electrostatic spinning, controlling the temperature of a receiving device to be 25-55 ℃, and controlling the rotating speed of the receiving device to be 20-100 n/min;
and step 3: calcining the obtained precursor nanofiber membrane in air atmosphere to obtain flexible TiO2A ceramic fiber membrane;
and 4, step 4: the obtained flexible TiO is mixed2And (3) contacting the ceramic fiber membrane with a metal lithium sheet in a vacuum atmosphere, and dropwise adding a solvent on the surface of the fiber membrane to obtain the flexible conductive titanium dioxide ceramic fiber membrane.
Dripping a solvent on the surface of the fiber membrane, and then adding TiO under the action of the solvent2Rapidly reacts with metallic lithium, and flexible TiO is found in 3s2The color of the ceramic fiber film is changed from white to black, the valence state of partial Ti is changed from +4 to +3, and TiO is caused2The electron conductivity of the ceramic fiber membrane increases.
The invention also provides a preparation method of the flexible conductive ceramic fiber membrane, which is characterized by comprising the following steps:
step 1: preparing an oxide ceramic fiber precursor solution;
step 2: performing electrostatic spinning on the obtained oxide ceramic fiber precursor solution to obtain a precursor nanofiber membrane, applying a constant-temperature thermal field of 25-55 ℃ in a spinning interval during electrostatic spinning, controlling the temperature of a receiving device to be 25-55 ℃, and controlling the rotating speed of the receiving device to be 20-100 n/min;
and step 3: calcining the obtained precursor nanofiber membrane in an air atmosphere to obtain a flexible ceramic fiber membrane;
and 4, step 4: and contacting the obtained flexible ceramic fiber membrane with a metal lithium sheet in a vacuum atmosphere, and dropwise adding a solvent on the surface of the fiber membrane to obtain the flexible conductive ceramic fiber membrane.
Preferably, the oxide is tin dioxide (SnO)2) Lanthanum Lithium Titanate (LLTO) or Barium Titanate (BTO).
Preferably, in the precursor solution, the mass ratio of the high molecular polymer to the solvent is 1: 10-1: 80.
preferably, the mass ratio of the high molecular polymer to the solvent is 1: 12-1: 80.
preferably, said TiO is2The preparation method of the precursor solution comprises the following steps: dissolving a high molecular polymer in a solvent at the temperature of 20-100 ℃, stirring for 30-480 min, then adding a titanium source, and stirring for 10-360 min to obtain TiO2And (3) precursor solution.
Preferably, the titanium source is at least one of titanium trichloride, tetrabutyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate, titanyl acetylacetonate and tetraethyl titanate.
Preferably, the solvent is at least one of water, ethanol, ethylene glycol, isopropanol, glycerol, acetylacetone, glacial acetic acid and N, N-dimethylformamide.
Preferably, the high molecular polymer is at least one of polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl acetate, polyvinylidene fluoride and polyvinyl butyral.
Preferably, the parameters of the electrostatic spinning are as follows: the relative humidity is 20% -70%, the filling speed is 0.5-90 mL/h, the voltage is 8-50 kV, the distance between a receiving device and a spinning nozzle is 10-30 cm, and the receiving device is a metal roller.
Preferably, said calcining comprises: gradually heating from room temperature to 600-1000 ℃, wherein the heating rate is 2-10 ℃/min, and keeping for 0-480 min at 600-1000 ℃.
Preferably, the solvent in step 4 is at least one of ethylene carbonate, ethylene glycol dimethyl ether, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, methyl ethyl carbonate and 1, 3-dioxolane.
Preferably, the flexible TiO2The average diameter of the fibers in the ceramic fiber membrane is 100-450 nm, the relative standard deviation is 1-5%, the internal crystal grain size is 10-100 nm, and TiO2The softness of the ceramic fiber membrane is 10-70 mN. The fiber diameter range shows that the fiber diameter is smaller, the single fiber has better softness, and the improvement of the fiber membrane is facilitatedThe softness of (c); the relative standard deviation is used for representing the uniformity of fiber diameter distribution, and the smaller the deviation value is, the better the fiber uniformity is; the grain size is closely related to the mechanical properties of the fibrous film.
The invention relates to a controllable preparation method, and the strength, the softness and the fineness of a flexible conductive titanium dioxide ceramic fiber membrane and the fineness of fibers can be regulated and controlled by voltage, spinning distance, roller rotating speed, heating rate in the calcining process and calcining temperature in the electrostatic spinning process.
The invention also provides the flexible conductive titanium dioxide ceramic fiber membrane prepared by the preparation method.
The invention firstly prepares the flexible white non-conductive TiO2Ceramic fibre membrane, then proposes ultra-fast reduction of TiO at normal temperature2Method for increasing the conductivity of TiO2Conversion of ceramic nanofiber membranes to black conductive TiO2A ceramic fiber membrane. Prepared flexible and conductive black TiO2The ceramic fiber membrane can be used in the fields of energy sources and electronics such as photocatalysis, lithium battery electrode materials, microelectronic devices and the like.
Compared with the prior art, the invention has the following technical effects:
1. the invention prepares the flexible TiO by a simple electrostatic spinning method2Ceramic fiber (membrane) materials. The electrostatic spinning process has the advantages of simple and convenient fiber preparation equipment, short period and wide raw material adaptability, thereby reducing the production cost.
2. The invention is prepared by mixing flexible TiO2The ceramic fiber is lightly contacted with the metal lithium sheet, and TiO can be rapidly reduced within 3s2To obtain black conductive TiO with unique electrical, optical and mechanical properties2. The method saves energy consumption and improves time efficiency.
3. Existing TiO2The ceramic material is composed of discrete micro-particles, and has poor mechanical and interface electrochemical properties; the invention prepares flexible TiO2The ceramic fiber membrane still has good flexibility after being reduced, and is beneficial to application in the field of energy intelligence and wearability.
4. The invention adopts cheap organic solventAgent as catalyst for reducing TiO by using metallic lithium sheet2The ceramic material improves the electronic conductivity of the material and has potential application in lithium batteries.
5. The preparation method is carried out at normal temperature, the process is very quick, energy and time are saved, and the prepared conductive black TiO is2The ceramic fiber membrane has large specific surface area and good mechanical flexibility, and has potential application in the fields of photocatalysis, electrocatalysis in the field of energy, battery electrode materials and the like.
6. The invention is also applicable to tin dioxide (SnO)2) The ceramic fiber membrane has the advantages of wide application range, simple process and low cost.
Drawings
FIG. 1 shows TiO before and after reduction of prepared lithium2Physical picture of the membrane.
FIG. 2 shows reduced TiO prepared according to the present invention2Graph of conductivity change of the membrane.
FIG. 3 shows the reduced TiO prepared according to the present invention2The film is used as a lead to light the LED lamp object picture.
FIG. 4 shows TiO prepared according to the present invention2XRD pattern of the film.
FIG. 5 shows TiO prepared according to the present invention2SEM spectra of the membrane.
FIG. 6 shows TiO prepared according to the present invention2TEM spectra of the films.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Each raw material used in the following examples is a commercially available product.
Example 1
A preparation method of a flexible conductive titanium dioxide ceramic fiber membrane comprises the following specific steps:
(1) preparing TiO consisting of a titanium source, a high molecular polymer and a solvent2Precursor solution: dissolving high molecular polymer polyethylene oxide (0.5 g, Latin, P101341) in glacial acetic acid 4g at 30 deg.C, stirring for 120min, adding ethanol 8g and isopropyl titanate 1.5g, and stirring to obtain TiO2And (3) precursor solution.
(2) The obtained TiO is mixed2Performing electrostatic spinning on the precursor solution, wherein under the action of an electric field, the repulsion force of the surface charges of the charged droplets exceeds the surface tension thereof, a jet flow is formed from the surface, and the jet flow is finally deposited on a receiving substrate through a series of processes of stretching, solvent volatilization, polymer solution jet flow solidification and the like to obtain a precursor nanofiber membrane, wherein a constant-temperature thermal field of 25 ℃ is applied in a spinning interval during electrostatic spinning, and the temperature of a receiving device is controlled to be 25 ℃; the parameters of electrostatic spinning are as follows: the relative humidity is 45%, the filling speed is 3mL/h, the voltage is 20kV, the distance between a receiving device and a spinning nozzle is 20cm, the rotating speed of the receiving device is 60n/min, and the receiving device is a metal roller.
(3) Calcining the obtained precursor nanofiber membrane in air atmosphere to obtain flexible TiO2Ceramic fiber membrane, calcining refers to gradually raising the temperature from room temperature (25 ℃) to 800 ℃, the rate of temperature rise is 5 ℃/min, and the temperature is maintained at 800 ℃ for 120 min.
The TiO is2The average diameter of the ceramic fiber membrane is 325nm, the relative standard deviation is 2%, the internal crystal grain size is 50nm according to the Scherrer formula, and the TiO is measured by a softness tester2The softness of the ceramic fiber film was 11 mN.
(4) The obtained flexible TiO is mixed2The ceramic fiber membrane is contacted with a metal lithium sheet in a vacuum atmosphere, 10 microliter of DMF is dripped on the surface of the fiber membrane, and the mixture passes through 3-10S and white TiO2The ceramic fiber membrane turned completely black.
(5) The TiO thus obtained is simply washed with the solvent used above2Removing residual impurities on the surface of the ceramic fiber film, then drying in vacuum, removing the solvent to obtain the conductive black TiO2A ceramic fiber membrane.
Example 2
A preparation method of a flexible conductive titanium dioxide ceramic fiber membrane comprises the following specific steps:
(1) preparing TiO consisting of a titanium source, a high molecular polymer and a solvent2Precursor solution: dissolving high molecular polymer polyethylene oxide (0.5 g, Latin, P101341) in glacial acetic acid 4g at 30 deg.C, stirring for 120min, adding ethanol 8g and isopropyl titanate 1.5g, and stirring to obtain TiO2And (3) precursor solution.
(2) The obtained TiO is mixed2Performing electrostatic spinning on the precursor solution to form a precursor nanofiber membrane, and applying a constant-temperature thermal field of 25 ℃ in a spinning interval during electrostatic spinning and controlling the temperature of a receiving device to be 25 ℃; the parameters of electrostatic spinning are as follows: the relative humidity is 45%, the filling speed is 3mL/h, the voltage is 20kV, the distance between a receiving device and a spinning nozzle is 20cm, the rotating speed of the receiving device is 60n/min, and the receiving device is a metal roller.
(3) Calcining the obtained precursor nanofiber membrane in air atmosphere to obtain flexible TiO2Placing the precursor fiber film in air atmosphere to calcine to obtain TiO2The ceramic fiber membrane is calcined, wherein the calcining temperature is gradually increased from room temperature (25 ℃) to 800 ℃, the heating rate is 5 ℃/min, and the calcining temperature is kept for 120min at 800 ℃.
The TiO is2The average diameter of the ceramic fiber membrane is 325nm, the relative standard deviation is 2%, the internal crystal grain size is 50nm according to the Scherrer formula, and the TiO is measured by a softness tester2The softness of the ceramic fiber film was 11 mN.
(4) The obtained flexible TiO is mixed2The ceramic fiber membrane was brought into contact with a lithium metal plate under vacuum, and 10. mu.l of DMF, NMP, DMAc, 10. mu.l of a mixed solvent of DMC and EC (DMC: EC: 1 by volume) and 10. mu.l of a mixed solvent of DME and DOL (DME: DOL: 1 by volume) were added dropwise to the surface of the fiber membrane, and similarly, white TiO2The ceramic fiber film rapidly darkens in all solvents, however, TiO acting with different solvents2The rate of blackening of the ceramic fiber membrane is different.
(5) Respectively using the above-mentioned solvents to simply clean respectively reduced TiO2Removing residual impurities on the surface of the ceramic fiber membrane, then drying in vacuum, removing the solvent to obtain the conductive black TiO treated by different solvents2A ceramic fiber membrane.
(6) The obtained black TiO treated by different solvents2The ceramic fiber membrane was subjected to conductivity measurement, and found to be TiO2The conductivity of the ceramic fiber membranes is different, in the case of NMP, TiO2The ceramic fiber membrane has the lowest conductivity, and when a DME and DOL mixed solvent is adopted, TiO2The ceramic fiber membranes have the highest electrical conductivity.
Example 3
A preparation method of a flexible conductive oxide ceramic fiber membrane comprises the following specific steps:
(1) preparing SnO consisting of tin source, high-molecular polymer and solvent2Precursor solution: dissolving 2g of high molecular polymer polyvinyl alcohol (Aladdin, polyvinyl alcohol 1788 type) in 18g of water at 30 deg.C, stirring at 90 deg.C for 120min, cooling to room temperature, collecting 10g of PVA solution, slowly adding 1g of SnCl into the solution4·5H2O, adding water and stirring simultaneously, adjusting the mass fraction of PVA to be 6 percent, and forming uniformly mixed SnO2Precursor solution;
(2) the obtained SnO2Performing electrostatic spinning on the precursor solution, wherein under the action of an electric field, the repulsion force of the surface charges of the charged droplets exceeds the surface tension thereof, a jet flow is formed from the surface, and the jet flow is finally deposited on a receiving substrate through a series of processes of stretching, solvent volatilization, polymer solution jet flow solidification and the like to obtain a precursor nanofiber membrane, wherein a constant-temperature thermal field of 25 ℃ is applied in a spinning interval during electrostatic spinning, and the temperature of a receiving device is controlled to be 25 ℃; the parameters of electrostatic spinning are as follows: the relative humidity is 45%, the filling speed is 1mL/h, the voltage is 20kV, the distance between a receiving device and a spinning nozzle is 20cm, the rotating speed of the receiving device is 60n/min, and the receiving device is a metal roller;
(3) calcining the obtained precursor nanofiber membrane in air atmosphere to obtain flexible SnO2The ceramic fiber membrane is calcined, namely the temperature is gradually increased from room temperature (25 ℃) to 800 ℃, and the temperature is increasedThe rate was 10 ℃/min and held at 800 ℃ for 480 min.
Said SnO2The average diameter of the ceramic fiber membrane is 500nm, the relative standard deviation is 2%, the internal crystal grain size is 70nm according to the Scherrer formula, and SnO is measured by a softness tester2The softness of the ceramic fiber film was 40 mN.
(4) The obtained flexible SnO2The ceramic fiber membrane is contacted with a metal lithium sheet in vacuum atmosphere, 10 microliter of DMF is dripped on the surface of the fiber membrane, and white SnO is added after 3-10S2The ceramic fiber film turned completely brown.
(5) Simply washing the obtained flexible SnO by using the solvent adopted2Removing residual impurities on the surface of the ceramic fiber film, then drying in vacuum, removing the solvent to obtain the flexible conductive brown SnO2A ceramic fiber membrane. Flexible SnO before reduction measured by four-probe method2The conductivity of the ceramic fiber membrane is 0.01mS/cm, and the flexible SnO is reduced2The conductivity of the ceramic fiber membrane is 300 mS/cm.
Example 4
A preparation method of a flexible conductive oxide ceramic fiber membrane comprises the following specific steps:
(1) preparing a BTO precursor solution consisting of a barium source, a titanium source, a high molecular polymer and a solvent: 0.6g of high molecular polymer polyvinylpyrrolidone (avastin, P110610) is dissolved in 9.4g of water at the temperature of 30 ℃, the mixture of glacial acetic acid and ethanol (the mass ratio is 1:1:1) is stirred for 60min, then 0.2554g of barium acetate and 0.3403g of tetrabutyl titanate are sequentially added, stirred for 120min and uniformly mixed to obtain a precursor solution.
(2) Preparing a precursor fiber film from the precursor solution by an electrostatic spinning method, and applying a constant-temperature thermal field of 25 ℃ in a spinning interval during electrostatic spinning; the parameters of electrostatic spinning are as follows: the relative humidity is 45%, the filling speed is 1mL/h, the voltage is 15kV, the distance between the receiving device and the spinning nozzle is 15cm, the distance between the sliding table device is 6cm, the rotating speed of the receiving device is 60n/min, and the receiving device is a metal roller.
(3) And calcining the obtained precursor nanofiber membrane in an air atmosphere to obtain the flexible BTO ceramic fiber membrane, wherein the calcining refers to gradually increasing the temperature from room temperature (25 ℃) to 800 ℃, the temperature increase rate is 5 ℃/min, and the flexible BTO ceramic fiber membrane is kept at 800 ℃ for 240 min.
The average diameter of the BTO ceramic fiber membrane is 300nm, the relative standard deviation is 2%, the internal crystal grain size is (24nm) obtained through a Scherrer formula, and the softness of the BTO ceramic fiber membrane is 30mN measured through a softness tester.
(4) The obtained flexible BTO ceramic fiber membrane is contacted with a lithium metal sheet in a vacuum atmosphere, 10 microliters of DMF is dripped on the surface of the fiber membrane, and the white BTO ceramic fiber membrane is completely changed into black after 3-10 seconds.
(5) And (3) simply cleaning the obtained flexible BTO ceramic fiber membrane by using the solvent, removing residual impurities on the surface, then drying in vacuum, and removing the solvent to obtain the flexible conductive black BTO ceramic fiber membrane. The conductivity of the flexible BTO ceramic fiber membrane before reduction is 0mS/cm and the conductivity of the flexible BTO ceramic fiber membrane after reduction is 200mS/cm measured by a four-probe method.
Example 5
A preparation method of a flexible conductive oxide ceramic fiber membrane comprises the following specific steps:
(1) preparing a LLTO precursor solution consisting of a lithium source, a lanthanum source, a titanium source, a high-molecular polymer and a solvent: 0.68g of polyethylene oxide (Aladdin, P101341) is dissolved in 7.2g of N, N-dimethylformamide and 0.68g of glacial acetic acid at the temperature of 30 ℃, then lithium source lithium chloride, lanthanum source lanthanum chloride and titanium source tetrabutyl titanate are sequentially added, stirred for 120min and uniformly mixed to obtain a precursor solution, wherein the molar ratio of the lithium source, the lanthanum source, the titanium source, the high-molecular polymer and the solvent in the solution is 0.33:0.55:1:0.04:260: 940.
(2) Preparing a precursor fiber film from the precursor solution by an electrostatic spinning method, and applying a constant-temperature thermal field of 25 ℃ in a spinning interval during electrostatic spinning; the parameters of electrostatic spinning are as follows: the relative humidity is 45%, the filling speed is 1.5mL/h, the voltage is 15kV, the distance between the receiving device and the spinning nozzle is 20cm, the rotating speed of the receiving device is 40n/min, and the receiving device is a metal roller.
(3) And calcining the obtained precursor nanofiber film in an air atmosphere to obtain the flexible LLTO ceramic fiber film, wherein the calcining refers to gradually increasing the temperature from room temperature (25 ℃) to 800 ℃, the temperature increasing rate is 5 ℃/min, and the temperature is kept at 800 ℃ for 120 min.
The average diameter of the LLTO ceramic fiber film is 300nm, the relative standard deviation is 2%, the internal grain size is 50nm according to the Scherrer formula, and the softness of the LLTO ceramic fiber film is 50mN measured by a softness tester.
(4) And contacting the obtained flexible LLTO ceramic fiber membrane with a metal lithium sheet in a vacuum atmosphere, dropwise adding 10 microliters of DMF (dimethyl formamide) on the surface of the fiber membrane, and completely turning the white LLTO ceramic fiber membrane into black after 3-10 seconds.
(5) And (3) simply cleaning the obtained flexible LLTO ceramic fiber film by using the adopted solvent, removing residual impurities on the surface, then drying in vacuum, and removing the solvent to obtain the flexible conductive black LLTO ceramic fiber film. The conductivity of the flexible LLTO ceramic fiber membrane before reduction is 0mS/cm and the conductivity of the flexible LLTO ceramic fiber membrane after reduction is 100mS/cm measured by a four-probe method.
Test example 1:
a photograph of the flexible conductive titania ceramic fiber membrane provided in example 1 is taken, and as shown in FIG. 1, it can be seen from FIG. 1 that the original titania ceramic fiber membrane provided in example 1 is white, and the reduced titania ceramic fiber membrane is black.
Test example 2:
the conductivity of the flexible titania ceramic fiber membrane provided in example 1 was measured, and as shown in fig. 2, the conductivity of the initial titania ceramic fiber membrane was almost 0, and after the reduction in the step (4) of example 1, the conductivity was greatly increased, and the conductivity was different with the change of time.
Test example 3:
the flexible conductive titanium dioxide ceramic fiber film provided in example 1 was assembled into a circuit for photographing, as shown in fig. 3, the flexible conductive titanium dioxide ceramic fiber film was used as a part of a wire, and an LED lamp was turned on, indicating that the prepared black titanium dioxide ceramic fiber film was conductive.
Test example 4:
the XRD test of the titania ceramic fiber film provided in example 1 was carried out, and the obtained spectrum is shown in fig. 4, and it can be seen from fig. 4 that the original titania ceramic fiber film and the conductive titania ceramic fiber film have similar structures, which are anatase type, and it is shown that the crystal structure of the ceramic fiber film is not damaged by the reduction.
Test example 5:
the flexible conductive titania ceramic fiber membrane provided in example 1 was subjected to SEM test, and the obtained spectrum is shown in fig. 5, from which it can be seen that the ceramic fiber membrane is composed of a plurality of ceramic nanofibers.
Test example 6:
the flexible conductive titanium dioxide ceramic fiber film in example 1 was subjected to TEM test, and the obtained spectrum is shown in fig. 6, as can be seen from fig. 6, the TiO in the flexible conductive titanium dioxide ceramic fiber film2The diameter of the surface of the ceramic nanofiber is about 300 nm.
Claims (8)
1. A preparation method of a flexible conductive titanium dioxide ceramic fiber membrane is characterized by comprising the following steps:
step 1: preparing TiO2A precursor solution, wherein the precursor solution contains a titanium source, a high molecular polymer and a solvent;
step 2: the obtained TiO is mixed2Performing electrostatic spinning on the precursor solution to obtain a precursor nanofiber membrane, applying a constant-temperature thermal field of 25-55 ℃ in a spinning interval during electrostatic spinning, controlling the temperature of a receiving device to be 25-55 ℃, and controlling the rotating speed of the receiving device to be 20-100 n/min;
and step 3: calcining the obtained precursor nanofiber membrane in air atmosphere to obtain flexible TiO2A ceramic fiber membrane;
and 4, step 4: the obtained flexible TiO is mixed2The ceramic fiber membrane is contacted with a metal lithium sheet in a vacuum atmosphere, and a solvent is dripped on the surface of the fiber membrane to obtain a flexible conductive titanium dioxide ceramic fiber membrane; the solvent in the step 4 is ethylene carbonate, ethylene glycol dimethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylAt least one of pyrrolidone, methyl ethyl carbonate and 1, 3-dioxolane.
2. The method for preparing a flexible conductive titanium dioxide ceramic fiber film according to claim 1, wherein the mass ratio of the high molecular polymer to the solvent in the precursor solution is 1: 10-1: 80.
3. the method of claim 1, wherein the TiO is selected from the group consisting of titanium dioxide, and titanium dioxide2The preparation method of the precursor solution comprises the following steps: dissolving a high molecular polymer in a solvent at the temperature of 20-100 ℃, stirring for 30-480 min, then adding a titanium source, and stirring for 10-360 min to obtain TiO2And (3) precursor solution.
4. The method for preparing a flexible conductive titanium dioxide ceramic fiber membrane according to claim 1, wherein in the step 1, the titanium source is at least one of titanium trichloride, tetrabutyl titanate, isopropyl titanate, titanium tetrachloride, titanyl sulfate, titanyl acetylacetonate, and tetraethyl titanate; the solvent is at least one of water, ethanol, glycol, isopropanol, glycerol, acetylacetone, glacial acetic acid and N, N-dimethylformamide; the high molecular polymer is at least one of polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl acetate, polyvinylidene fluoride and polyvinyl butyral.
5. The method for preparing a flexible conductive titanium dioxide ceramic fiber membrane according to claim 1, wherein the parameters of the electrostatic spinning are as follows: the relative humidity is 20% -70%, the filling speed is 0.5-90 mL/h, the voltage is 8-50 kV, the distance between a receiving device and a spinning nozzle is 10-30 cm, and the receiving device is a metal roller.
6. The method of preparing a flexible conductive titania ceramic fiber membrane according to claim 1, wherein the calcining comprises: gradually heating from room temperature to 600-1000 ℃, wherein the heating rate is 2-10 ℃/min, and keeping for 0-480 min at 600-1000 ℃.
7. The method of claim 1, wherein the flexible TiO ceramic fiber membrane is prepared by a method comprising2The average diameter of the fibers in the ceramic fiber membrane is 100-450 nm, the relative standard deviation is 1-5%, the internal crystal grain size is 10-100 nm, and TiO2The softness of the ceramic fiber membrane is 10-70 mN.
8. A method for preparing a flexible conductive ceramic fiber membrane is characterized by comprising the following steps:
step 1: preparing an oxide ceramic fiber precursor solution; the oxide is tin dioxide, lithium lanthanum titanate or barium titanate;
step 2: performing electrostatic spinning on the obtained oxide ceramic fiber precursor solution to obtain a precursor nanofiber membrane, applying a constant-temperature thermal field of 25-55 ℃ in a spinning interval during electrostatic spinning, controlling the temperature of a receiving device to be 25-55 ℃, and controlling the rotating speed of the receiving device to be 20-100 n/min;
and step 3: calcining the obtained precursor nanofiber membrane in an air atmosphere to obtain a flexible ceramic fiber membrane;
and 4, step 4: contacting the obtained flexible ceramic fiber membrane with a metal lithium sheet in a vacuum atmosphere, and dropwise adding a solvent on the surface of the fiber membrane to obtain a flexible conductive ceramic fiber membrane; the solvent in the step 4 is at least one of ethylene carbonate, ethylene glycol dimethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, ethyl methyl carbonate and 1, 3-dioxolane.
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| CN113737395A (en) * | 2021-08-06 | 2021-12-03 | 华南理工大学 | Flexible titanium dioxide nanofiber membrane and preparation method and application thereof |
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| CN115369570A (en) * | 2022-06-30 | 2022-11-22 | 东南大学 | Device and method for continuously producing flexible oxide nanofiber membrane |
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