WO2024027076A1 - Preparation method for flexible polyimide/titanium mesh film composite electrode material, product and use thereof - Google Patents
Preparation method for flexible polyimide/titanium mesh film composite electrode material, product and use thereof Download PDFInfo
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- WO2024027076A1 WO2024027076A1 PCT/CN2022/139572 CN2022139572W WO2024027076A1 WO 2024027076 A1 WO2024027076 A1 WO 2024027076A1 CN 2022139572 W CN2022139572 W CN 2022139572W WO 2024027076 A1 WO2024027076 A1 WO 2024027076A1
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- titanium mesh
- polyamic acid
- electrode material
- polyimide
- composite electrode
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229920001721 polyimide Polymers 0.000 title claims abstract description 71
- 239000004642 Polyimide Substances 0.000 title claims abstract description 64
- 239000007772 electrode material Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000010409 thin film Substances 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 52
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 47
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 34
- 150000004985 diamines Chemical class 0.000 claims description 26
- 238000006068 polycondensation reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003618 dip coating Methods 0.000 claims description 14
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 claims description 4
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 4
- -1 BAPP diamine Chemical class 0.000 claims 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- BCJIMAHNJOIWKQ-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-4-yl)oxy]-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2OC1=CC=CC2=C1C(=O)OC2=O BCJIMAHNJOIWKQ-UHFFFAOYSA-N 0.000 description 1
- KJLPSBMDOIVXSN-UHFFFAOYSA-N 4-[4-[2-[4-(3,4-dicarboxyphenoxy)phenyl]propan-2-yl]phenoxy]phthalic acid Chemical compound C=1C=C(OC=2C=C(C(C(O)=O)=CC=2)C(O)=O)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 KJLPSBMDOIVXSN-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the invention relates to the field of electrode material preparation, and specifically relates to a preparation method of a flexible polyimide/titanium mesh thin film composite electrode material, as well as its products and electrocatalytic applications.
- Flexible electrode is a material with high reliability and excellent flexibility. It has the advantages of light weight and easy bending. It perfectly fits the development theme of thinning, lightness and miniaturization. How to prepare flexible electrodes has become a matter of great significance. technical difficulties.
- Polyimide is a type of polymer containing an imide ring (-CO-N-CO-) in the main chain. It is one of the organic polymer materials with the best comprehensive properties.
- Flexible polyimide has high temperature resistance and corrosion resistance, and can show excellent flexibility and can freely deform according to the shape of the laying carrier, thus improving the flexibility of this type of material in practical applications.
- Titanium mesh is a commonly used anode electrode material. It has corrosion resistance, long life, high current density during operation, small overpotential, and high electrode catalytic activity, which can effectively improve production efficiency.
- the invention patent CN201710183535 reports a method for preparing a modified titanium mesh electrode for water splitting and oxygen production (OER). This method performs cobalt selenide coating on the surface of the titanium mesh to construct a selenide electrode with an ohmic contact interface. Cobalt/titanium mesh splits water to produce oxygen composite electrode; however, the catalyst materials are all hard metal materials, and their high processing difficulty greatly limits the application scenarios of oxygen evolution reaction.
- the purpose of the invention is to disclose a method for preparing a flexible polyimide/titanium mesh thin film composite electrode material.
- Another object of the present invention is to provide the polyimide/titanium mesh composite electrode material prepared by the above method.
- Another object of the present invention is to provide the application of electrocatalytic water splitting and oxygen production of the product.
- the object of the present invention is achieved through the following solution: a method for preparing a flexible polyimide/titanium mesh film composite electrode material, a flexible polyimide/titanium mesh composite electrode material constructed with titanium mesh as a skeleton, including the following steps:
- the first step is the preparation of polyamic acid: put diamine monomer, dianhydride monomer and solvent into a beaker and mix them. When the viscosity of the solution reaches 350-450 poise, the obtained polyamic acid solution can be used for coating. Coating treatment; the molar ratio of the dianhydride monomer to the diamine monomer is 2:1 to 1:2, and the diamine monomer includes diamine represented by chemical formula (1) and chemical formula (2). Amine monomer; the chemical formulas (1) and (2) are:
- R 1 and R 2 in the chemical formula (1) are respectively C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
- R 3 is -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 )n 1 -, or -O(CH 2 )n 2 O-, n 1 and n 2 are natural numbers from 1 to 10 respectively;
- the second step, dip coating and closed-loop polycondensation cut the titanium mesh with a thickness of 0.04 ⁇ 1mm and aperture of 0.3 ⁇ 0.5mm into a square of 5cm*5cm; after polishing the oxide layer on the surface of the titanium mesh, immerse it into the first step In the prepared polyamic acid solution, take out the titanium mesh after immersing it for half an hour, and remove excess polyamic acid resin with a scraper until the thickness of the resin coating attached to the titanium mesh is controlled to 3 to 5 ⁇ m. Then, coat the titanium mesh.
- the polyamic acid on the surface undergoes a closed-loop polycondensation reaction, that is, imidization is performed on the surface of the titanium mesh to obtain a flexible polyimide/titanium mesh thin film composite electrode material.
- the present invention selects titanium mesh with good conductivity and recyclability as the supporting material, and provides a method for preparing a flexible polyimide/titanium mesh composite electrode material constructed with titanium mesh as a skeleton.
- the method of the present invention prepares polyimide molecules with suitable energy band structures into polyimide nanolayer composite titanium mesh electrodes.
- Polyimide as a semiconductor material, forms a dense flexible Mott-Schottky contact layer with the titanium mesh. Under the condition of controlling the thickness to a certain level, the charge transfer efficiency can be improved, and it has high electrocatalytic oxygen evolution reaction activity.
- the dianhydride monomers are at least: pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), bisphenol A-type diether dianhydride (BPADA), benzophenone tetracarboxylic dianhydride (BPADA), One or a combination of two or more of carboxylic dianhydride, oxydiphthalic anhydride, and diphenylsulfone-3,4,3,4'-tetracarboxylic acid;
- PMDA pyromellitic dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- BPADA bisphenol A-type diether dianhydride
- BPADA benzophenone tetracarboxylic dianhydride
- carboxylic dianhydride oxydiphthalic anhydride
- diphenylsulfone-3,4,3,4'-tetracarboxylic acid diphenylsulfone
- the diamine monomer is at least: 4,4'-diamino-2,2'-dimethylbiphenyl (m-tolidine), 2,2-bis[4-(4-aminophenoxy) One or a combination of two or more of phenyl]propane (BAPP) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP).
- the molar ratio of the dianhydride monomer to the diamine monomer is 1:1; the diamine monomer and the dianhydride monomer are mixed to produce polyamic acid, and the organic polar solvent N,N-dimethyl is added.
- Formamide (DMF) is a polyamic acid solution that meets the usage requirements in the viscosity range of 350 to 450 poise.
- the titanium mesh is a stamped titanium mesh with a thickness ranging from 0.04 to 1 mm and a mesh aperture ranging from 0.3 to 0.5 mm.
- the temperature range of the closed-ring polycondensation reaction is 200-400°C, and the reaction time is 8-12 hours.
- the invention discloses a preparation method, product and application of a flexible polyimide electrode material with titanium mesh as a skeleton.
- Polyimide molecules with suitable structure are used as a semiconductor material and titanium mesh to form a dense flexible Mott-Schottky
- the catalyst material under the condition that the thickness is controlled to a certain extent, is related to its application as an anode electrode in the electrolysis of water to generate oxygen.
- the aliphatic portions of R 1 , R 2 and R 3 can provide non-polar functional groups for the polyimide film and provide a higher degree of flexibility, thereby reducing the defective rate in the film-forming process and thus ensuring the preparation Develop flexible and suitable electrode materials that have good processability.
- the dianhydride monomers also include: pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPADA), 2,2-bis[4-(3,4-di Carboxyphenoxy)phenyl]propane dianhydride (BPADA), benzophenone tetracarboxylic dianhydride, oxybisphthalic anhydride, and diphenylsulfone-3,4,3,4'-tetracarboxylic At least one of the acid dianhydride compositions; the diamine monomer also includes: 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 2,2-bis[ One or more of 4-(4-aminophenoxy)phenyl]propane (BAPP) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane.
- PMDA pyromellitic dianhydride
- BPADA bipheny
- the molar ratio of the dianhydride monomer to the diamine monomer is 1:1; the diamine monomer and the dianhydride monomer are mixed to produce polyamic acid, and the organic polar solvent N,N-dimethylformamide ( DMF), when the viscosity reaches the range of 350 to 450 poise, the polyamic acid solution meets the usage requirements.
- DMF organic polar solvent N,N-dimethylformamide
- the invention also provides a preparation method, products and applications of a flexible polyimide/titanium mesh thin film composite electrode material, and the electrode material prepared according to the above method.
- the present invention also provides the application of the flexible polyimide/titanium mesh thin film composite electrode material in electrocatalysis, especially as an anode electrode in the electrolysis of water to generate oxygen.
- the present invention provides a new approach to the development and preparation of catalysts for electrocatalytic oxygen evolution reaction.
- the invention discloses a preparation method of a flexible polyimide/titanium mesh composite electrode material with a simple preparation process, which is simple and easy to control and can realize large-scale production.
- the invention uses polyimide molecules with suitable structure as a semiconductor material and titanium mesh to form a dense flexible Mott-Schottky catalyst material, which has a higher degree of flexibility. Under the condition of controlling the thickness to a certain extent, it can be used as an electrolytic water to produce oxygen. Application as anode electrode in reactions.
- the aliphatic portions of R 1 , R 2 and R 3 can provide non-polar functional groups for the polyimide film, ensuring the preparation of flexible and suitable electrode materials with good processability.
- Dianhydride monomers pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), bisphenol A-type diether dianhydride (BPADA);
- PMDA pyromellitic dianhydride
- BPDA biphenyltetracarboxylic dianhydride
- BPADA bisphenol A-type diether dianhydride
- Diamine monomer 4,4'-diamino-2,2'-dimethylbiphenyl (m-tolidine), 2,2-bis[4-(4-aminophenoxy)phenyl]propane ( BAPP), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), mix according to Table 1 to prepare polyamic acid emulsion.
- BAPP 2,2-bis[4-(4-aminophenoxy)phenyl]propane
- HFBAPP 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane
- a flexible polyimide/titanium mesh film composite electrode material is prepared according to the following steps:
- the first step is the preparation of polyamic acid:
- the second step is titanium mesh infiltration and closed-loop polycondensation: cut a specific titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with polyamic acid solution. cloth treatment, and use a scraper to control the coating thickness to 3 ⁇ m; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform closed-loop polycondensation at 250°C After 8 hours of reaction, the thickness of the polyimide coating is about 200nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film. The obtained polyimide/titanium mesh composite material has good flexibility. A flexible polyimide/titanium mesh composite electrode material was obtained.
- the electrode has a current density of 1.8V at a voltage of 1.8V. It can reach 5mA/cm 2 . When the voltage only increases to 1.9V, the current density can increase to 15mA/cm 2 and the current density can be maintained at a high level. Therefore, this electrode material shows better electrocatalytic performance.
- a flexible polyimide carbon/titanium mesh composite electrode material is similar to the steps in Example 1 and is prepared as follows:
- the first step is the preparation of polyamic acid:
- the second step is titanium mesh infiltration and closed-loop polycondensation: cut a specific titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with polyamic acid solution. cloth treatment, and use a scraper to control the coating thickness to 4 ⁇ m; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform closed-loop polycondensation at 300°C After 8 hours of reaction, the thickness of the polyimide coating is about 300nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film. The obtained polyimide/titanium mesh composite material has good flexibility. A flexible polyimide/titanium mesh composite electrode material is obtained, which is easy to process.
- a flexible polyimide/titanium mesh thin film composite electrode material is similar to the steps in Example 1 and is prepared as follows:
- the first step is the preparation of polyamic acid: add diamine monomer and dianhydride monomer according to the proportion in Table 1, stir and dissolve in 100 ml of N,N-dimethylformamide (DMF), molar concentration (mol% )for:
- DMF N,N-dimethylformamide
- the second step is titanium mesh infiltration and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with a polyamic acid solution. , and control the coating thickness to 5 ⁇ m through a scraper; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform a closed-loop polycondensation reaction at 300°C 8 hour, the thickness of the polyimide coating is about 400nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film.
- the obtained polyimide/titanium mesh composite material has good flexibility and obtains a A flexible polyimide/titanium mesh composite electrode material that is easy to process.
- a flexible polyimide/titanium mesh thin film composite electrode material is similar to the steps in Example 1 and is prepared as follows:
- the first step is the preparation of polyamic acid: add diamine monomers m-tolidine and BAPP, dianhydride monomers PMDA and BPADA according to the proportions in Table 1, stir and dissolve in 100ml of N,N-dimethylformamide (DMF ), the molar concentration (mol%) is:
- the second step is titanium mesh infiltration and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with a polyamic acid solution. , and control the coating thickness to 3 ⁇ m through a scraper; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform a closed-loop polycondensation reaction at 250°C 8 hour, the coating thickness of the polyimide is about 300nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film. The obtained polyimide/titanium mesh composite material also has good flexibility, and the polyimide film is obtained. A flexible polyimide/titanium mesh composite electrode material.
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A preparation method for a flexible polyimide/titanium mesh film composite electrode material, a product and a use thereof. Polyimide molecules with a suitable band structure are used as a reactive active center to be compounded with a titanium mesh substrate to prepare a polyimide/titanium mesh composite coating. The process involves multiple steps, such as the preparation of polyamic acid, coating, closed-loop condensation reaction, and the like to finally obtain a polyimide/titanium mesh composite film oxygen production electrode. A thin film catalyst electrode having good performance is prepared after coating treatment. The polyimide molecules with a suitable structure are used as a semiconductor material to form a dense coating with the titanium mesh, and the Mott‑Schottky effect present at the interface enhances the electrocatalytic effect of the electrode, which serves as a use as an anode electrode in the electrolysis of water to produce oxygen. The prepared electrode material exhibits excellent flexibility and processability. Meanwhile, the electrode material also has characteristics such as high activity, good stability, and a straightforward manufacturing process, thereby suggesting the potential for achieving large-scale production.
Description
本发明涉及电极材料制备领域,具体涉及一种以柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法以及产品与电催化应用。The invention relates to the field of electrode material preparation, and specifically relates to a preparation method of a flexible polyimide/titanium mesh thin film composite electrode material, as well as its products and electrocatalytic applications.
柔性电极是一种具有高度可靠性和绝佳可挠性的材料,具有重量轻、易弯折等优势,完美地契合了轻薄化、小型化的发展主旋律,如何制备柔性电极成为了一个意义重大的技术难题。聚酰亚胺是一种主链上含有酰亚胺环(-CO-N-CO-)的一类聚合物,是综合性能最佳的有机高分子材料之一。柔性聚酰亚胺拥有耐高温性和耐腐蚀性,又可以表现出优异的柔顺性,可根据敷设载体的形状而发生自由形变,从而提高该类材料在实际应用过程中的使用灵活性。钛网是一种常用的阳极电极材料,它耐腐蚀,长寿命,工作时候电流密度高,过电位小,电极催化活性高,可有效提高生产效率。Flexible electrode is a material with high reliability and excellent flexibility. It has the advantages of light weight and easy bending. It perfectly fits the development theme of thinning, lightness and miniaturization. How to prepare flexible electrodes has become a matter of great significance. technical difficulties. Polyimide is a type of polymer containing an imide ring (-CO-N-CO-) in the main chain. It is one of the organic polymer materials with the best comprehensive properties. Flexible polyimide has high temperature resistance and corrosion resistance, and can show excellent flexibility and can freely deform according to the shape of the laying carrier, thus improving the flexibility of this type of material in practical applications. Titanium mesh is a commonly used anode electrode material. It has corrosion resistance, long life, high current density during operation, small overpotential, and high electrode catalytic activity, which can effectively improve production efficiency.
将聚酰亚胺柔性材料与钛网结合在一起,能够有效克服石墨电极和铅基合金电极的溶解问题,避免对电解液和阴极产造成污染,提高产品质量;同时柔性的聚酰亚胺材料能够保护钛电极发生的形变,兼具易弯曲和轻薄化等特点,是一类具有深远应用前景的电极材料。发明专利CN201710183535报道了一种用于分解水制氧(OER)的改性钛网电极的制备方法,该方法在钛网表面进行了硒化钴包覆处理,构建了具有欧姆接触界面的硒化钴/钛网分解水制氧复合电极;但是该催化剂材料选用的均为硬质属性的金属材料,高难加工性大大限制了析氧反应的应用场景。Combining polyimide flexible materials with titanium mesh can effectively overcome the dissolution problem of graphite electrodes and lead-based alloy electrodes, avoid contamination of electrolyte and cathode products, and improve product quality; at the same time, flexible polyimide materials It can protect the deformation of titanium electrodes and is easy to bend and thin. It is a type of electrode material with far-reaching application prospects. The invention patent CN201710183535 reports a method for preparing a modified titanium mesh electrode for water splitting and oxygen production (OER). This method performs cobalt selenide coating on the surface of the titanium mesh to construct a selenide electrode with an ohmic contact interface. Cobalt/titanium mesh splits water to produce oxygen composite electrode; however, the catalyst materials are all hard metal materials, and their high processing difficulty greatly limits the application scenarios of oxygen evolution reaction.
发明内容Contents of the invention
本发明的目的是公开了一种以柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法。The purpose of the invention is to disclose a method for preparing a flexible polyimide/titanium mesh thin film composite electrode material.
本发明的再一目的在于:提供上述方法制备的聚酰亚胺/钛网复合电极材料。Another object of the present invention is to provide the polyimide/titanium mesh composite electrode material prepared by the above method.
本发明的又一目的在于:提供所述产品的电催化水分解制氧的应用。Another object of the present invention is to provide the application of electrocatalytic water splitting and oxygen production of the product.
本发明目的通过下述方案实现:一种柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法,以钛网为骨架构建的柔性聚酰亚胺/钛网复合电极材料,包括如下 步骤:The object of the present invention is achieved through the following solution: a method for preparing a flexible polyimide/titanium mesh film composite electrode material, a flexible polyimide/titanium mesh composite electrode material constructed with titanium mesh as a skeleton, including the following steps:
第一步,聚酰胺酸的制备:在烧杯里投入二胺单体、二酐单体以及溶剂,进行混合,当溶液的黏度达到350~450泊时,得到的聚酰胺酸溶液即可用于涂覆处理;所述的二酐单体与二胺单体的摩尔比在2:1~1:2,所述的二胺单体,包含由化学式(1)和由化学式(2)表示的二胺单体;所述的化学式(1)、(2)为:The first step is the preparation of polyamic acid: put diamine monomer, dianhydride monomer and solvent into a beaker and mix them. When the viscosity of the solution reaches 350-450 poise, the obtained polyamic acid solution can be used for coating. Coating treatment; the molar ratio of the dianhydride monomer to the diamine monomer is 2:1 to 1:2, and the diamine monomer includes diamine represented by chemical formula (1) and chemical formula (2). Amine monomer; the chemical formulas (1) and (2) are:
其中,所述化学式(1)中R
1和R
2分别为C
1-C
6烷基或C
1-C
6烷氧基;
Wherein, R 1 and R 2 in the chemical formula (1) are respectively C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
所述化学式(2)中R
3为-C(CH
3)
2-、-C(CF
3)
2-、-(CH
2)n
1-、或者-O(CH
2)n
2O-,n
1和n
2分别为1至10的自然数;
In the chemical formula (2), R 3 is -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 )n 1 -, or -O(CH 2 )n 2 O-, n 1 and n 2 are natural numbers from 1 to 10 respectively;
第二步,浸涂与闭环缩聚:将厚度为0.04~1mm、孔径为0.3~0.5mm的钛网裁剪成5cm*5cm的正方形;将钛网表面氧化层进行打磨处理后,浸入到第一步配置好的聚酰胺酸溶液中,浸渍半小时后取出钛网,刮刀去掉多余的聚酰胺酸树脂,至附着在钛网上的树脂涂层厚度控制在3~5μm,接着,促使涂覆于钛网表面的聚酰胺酸发生闭环缩聚反应,即在钛网表面进行酰亚胺化,得到柔性聚酰亚胺/钛网薄膜复合电极材料。The second step, dip coating and closed-loop polycondensation: cut the titanium mesh with a thickness of 0.04~1mm and aperture of 0.3~0.5mm into a square of 5cm*5cm; after polishing the oxide layer on the surface of the titanium mesh, immerse it into the first step In the prepared polyamic acid solution, take out the titanium mesh after immersing it for half an hour, and remove excess polyamic acid resin with a scraper until the thickness of the resin coating attached to the titanium mesh is controlled to 3 to 5 μm. Then, coat the titanium mesh. The polyamic acid on the surface undergoes a closed-loop polycondensation reaction, that is, imidization is performed on the surface of the titanium mesh to obtain a flexible polyimide/titanium mesh thin film composite electrode material.
本发明针对OER反应活性和应用方面的不足,选用导电性良好且可以循环使用的钛网作为支撑材料,提供了以钛网为骨架构建的柔性聚酰亚胺/钛网复合电极材料的制备方法,本发明方法将能带结构适合的聚酰亚胺分子制备成聚酰亚胺纳米层复合钛网电极,聚酰亚胺作为一种半导体材料与钛网形成致密的柔性Mott-Schottky接触层,在控制厚度一定的情况下,电荷传输效率能够提升,具有较高的电催化析氧反应活性。Aiming at the deficiencies in OER reactivity and application, the present invention selects titanium mesh with good conductivity and recyclability as the supporting material, and provides a method for preparing a flexible polyimide/titanium mesh composite electrode material constructed with titanium mesh as a skeleton. , The method of the present invention prepares polyimide molecules with suitable energy band structures into polyimide nanolayer composite titanium mesh electrodes. Polyimide, as a semiconductor material, forms a dense flexible Mott-Schottky contact layer with the titanium mesh. Under the condition of controlling the thickness to a certain level, the charge transfer efficiency can be improved, and it has high electrocatalytic oxygen evolution reaction activity.
进一步的,所述的二酐单体至少为:均苯四甲酸二酐(PMDA)、联苯四甲酸二酐(BPDA)、双酚A型二醚二酐(BPADA)、二苯甲酮四羧酸二酐、氧双邻苯二甲酸酐、以及二苯基砜-3,4,3,4’-四羧酸二中的一种或二种以上的组合;Further, the dianhydride monomers are at least: pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), bisphenol A-type diether dianhydride (BPADA), benzophenone tetracarboxylic dianhydride (BPADA), One or a combination of two or more of carboxylic dianhydride, oxydiphthalic anhydride, and diphenylsulfone-3,4,3,4'-tetracarboxylic acid;
所述的二胺单体至少为:4,4’-二氨基-2,2’-二甲基联苯(m-tolidine)、2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(HFBAPP)中的一种或二种以上的组合。The diamine monomer is at least: 4,4'-diamino-2,2'-dimethylbiphenyl (m-tolidine), 2,2-bis[4-(4-aminophenoxy) One or a combination of two or more of phenyl]propane (BAPP) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP).
较优的,所述的二酐单体与二胺单体的摩尔比1:1;二胺单体和二酐单体混合产生聚酰胺酸,并且加有机极性溶剂N,N-二甲基甲酰胺(DMF),在黏度达到350~450泊范围内,达到使用要求的聚酰胺酸溶液。Preferably, the molar ratio of the dianhydride monomer to the diamine monomer is 1:1; the diamine monomer and the dianhydride monomer are mixed to produce polyamic acid, and the organic polar solvent N,N-dimethyl is added. Formamide (DMF) is a polyamic acid solution that meets the usage requirements in the viscosity range of 350 to 450 poise.
所述的钛网为厚度范围为0.04~1mm,网孔孔径范围为0.3~0.5mm的冲压钛网。The titanium mesh is a stamped titanium mesh with a thickness ranging from 0.04 to 1 mm and a mesh aperture ranging from 0.3 to 0.5 mm.
所述闭环缩聚反应的温度范围为200~400℃,反应时间为8~12h。The temperature range of the closed-ring polycondensation reaction is 200-400°C, and the reaction time is 8-12 hours.
本发明公开了一种钛网为骨架的柔性聚酰亚胺电极材料的制备方法及产品与应用,将结构适宜的聚酰亚胺分子作为一种半导体材料与钛网形成致密的柔性Mott-Schottky催化剂材料,在控制厚度一定的情况下,涉及到作为电解水制氧反应中作为阳极电极的应用。R
1、R
2和R
3的脂肪族部分能够为聚酰亚胺薄膜提供非极性的官能团,同时提供更高程度的柔韧性,从而使在成膜工艺中降低不良率,因而可以确保制备出柔性适合的电极材料,这具有良好的可加工性。
The invention discloses a preparation method, product and application of a flexible polyimide electrode material with titanium mesh as a skeleton. Polyimide molecules with suitable structure are used as a semiconductor material and titanium mesh to form a dense flexible Mott-Schottky The catalyst material, under the condition that the thickness is controlled to a certain extent, is related to its application as an anode electrode in the electrolysis of water to generate oxygen. The aliphatic portions of R 1 , R 2 and R 3 can provide non-polar functional groups for the polyimide film and provide a higher degree of flexibility, thereby reducing the defective rate in the film-forming process and thus ensuring the preparation Develop flexible and suitable electrode materials that have good processability.
在上述方案基础上,所述的二酐单体还包括:均苯四甲酸二酐(PMDA),联苯四甲酸二酐(BPADA)、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐(BPADA)、二苯甲酮四羧酸二酐、氧双邻苯二甲酸酐、以及二苯基砜-3,4,3,4’-四羧酸二酐组成中的至少一种;所述的二胺单体还包括:2,2'-二甲基-4,4'-二氨基联苯(m-tolidine)、2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷组成中的一种或多种。所述的二酐单体与二胺单体的摩尔比1:1;二胺单体和二酐单体混合产生聚酰胺酸,并且加有机极性溶剂N,N-二甲基甲酰胺(DMF),在黏度达到350~450泊范围内,即达到使用要求的聚酰胺酸溶液。Based on the above scheme, the dianhydride monomers also include: pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPADA), 2,2-bis[4-(3,4-di Carboxyphenoxy)phenyl]propane dianhydride (BPADA), benzophenone tetracarboxylic dianhydride, oxybisphthalic anhydride, and diphenylsulfone-3,4,3,4'-tetracarboxylic At least one of the acid dianhydride compositions; the diamine monomer also includes: 2,2'-dimethyl-4,4'-diaminobiphenyl (m-tolidine), 2,2-bis[ One or more of 4-(4-aminophenoxy)phenyl]propane (BAPP) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. The molar ratio of the dianhydride monomer to the diamine monomer is 1:1; the diamine monomer and the dianhydride monomer are mixed to produce polyamic acid, and the organic polar solvent N,N-dimethylformamide ( DMF), when the viscosity reaches the range of 350 to 450 poise, the polyamic acid solution meets the usage requirements.
本发明还提供了一种以柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法及产品与应用,根据上述方法制备得到的电极材料。The invention also provides a preparation method, products and applications of a flexible polyimide/titanium mesh thin film composite electrode material, and the electrode material prepared according to the above method.
本发明也提供了以柔性聚酰亚胺/钛网薄膜复合电极材料在电催化方面的应用,尤其作为电解水制氧反应中作为阳极电极的应用。The present invention also provides the application of the flexible polyimide/titanium mesh thin film composite electrode material in electrocatalysis, especially as an anode electrode in the electrolysis of water to generate oxygen.
本发明为电催化析氧反应的催化剂开发与制备提供了一种新的途径。The present invention provides a new approach to the development and preparation of catalysts for electrocatalytic oxygen evolution reaction.
本发明公开了一种制备工艺简单的柔性聚酰亚胺/钛网复合电极材料的制备方法,工艺简单易于控制并且可实现规模化生产。本发明将结构适宜的聚酰亚胺分子作为一种半导体材料与钛网形成致密的柔性Mott-Schottky催化剂材料,有更高程度的柔韧性,在控制厚度一定的情况下,作为电解水制氧反应中作为阳极电极的应用。R
1、R
2和R
3的脂肪族部分能够为聚酰亚胺薄膜提供非极性的官能团,可以确保制备出柔性适合的电极材料,这具有良好的可加工性。
The invention discloses a preparation method of a flexible polyimide/titanium mesh composite electrode material with a simple preparation process, which is simple and easy to control and can realize large-scale production. The invention uses polyimide molecules with suitable structure as a semiconductor material and titanium mesh to form a dense flexible Mott-Schottky catalyst material, which has a higher degree of flexibility. Under the condition of controlling the thickness to a certain extent, it can be used as an electrolytic water to produce oxygen. Application as anode electrode in reactions. The aliphatic portions of R 1 , R 2 and R 3 can provide non-polar functional groups for the polyimide film, ensuring the preparation of flexible and suitable electrode materials with good processability.
图1为实施例1所得的聚酰亚胺/钛网复合电极材料在氧饱和0.1M KOH溶液(pH=13.0)中测量的线性扫描伏安曲线。Figure 1 is a linear sweep voltammogram measured in an oxygen-saturated 0.1M KOH solution (pH=13.0) for the polyimide/titanium mesh composite electrode material obtained in Example 1.
材料准备:相应的二酐单体和二胺单体,其中,Material preparation: corresponding dianhydride monomer and diamine monomer, where,
二酐单体:均苯四甲酸二酐(PMDA)、联苯四甲酸二酐(BPDA)、双酚A型二醚二酐(BPADA);Dianhydride monomers: pyromellitic dianhydride (PMDA), biphenyltetracarboxylic dianhydride (BPDA), bisphenol A-type diether dianhydride (BPADA);
二胺单体:4,4’-二氨基-2,2’-二甲基联苯(m-tolidine)、2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(HFBAPP),按照表一投料混合,制备聚酰胺酸乳液。Diamine monomer: 4,4'-diamino-2,2'-dimethylbiphenyl (m-tolidine), 2,2-bis[4-(4-aminophenoxy)phenyl]propane ( BAPP), 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP), mix according to Table 1 to prepare polyamic acid emulsion.
表一二酐单体和二胺单体的混合涂料比例Table 1 Mixed coating ratio of dianhydride monomer and diamine monomer
实施例1:Example 1:
一种柔性聚酰亚胺/钛网薄膜复合电极材料,按如下步骤制备:A flexible polyimide/titanium mesh film composite electrode material is prepared according to the following steps:
第一步,聚酰胺酸的制备:The first step is the preparation of polyamic acid:
按照表一的比例投入二胺单体、二酐单体,搅拌溶解在100ml的N,N-二甲基甲酰胺(DMF)中,摩尔浓度(mol%)为:Add diamine monomer and dianhydride monomer according to the proportion in Table 1, stir and dissolve in 100 ml of N,N-dimethylformamide (DMF). The molar concentration (mol%) is:
BPADABPADA | PMDAPMDA | m-Tolidinem-Tolidine | BAPPBAPP |
6060 | 4040 | 6060 | 4040 |
在黏度达到400泊时结束聚合得到黏度适中的聚酰胺酸;When the viscosity reaches 400 poise, the polymerization is completed to obtain polyamic acid with moderate viscosity;
第二步,钛网浸润与闭环缩聚:将特定的钛网裁剪为5cm*5cm的正方形,采用砂纸打磨以除去表面的氧化层;接着采用浸涂法在钛网表面进行聚酰胺酸溶液的涂布处理,并通过刮刀控制涂覆的厚度在3μm;浸涂处理后放置在100℃的烘箱中干燥,接着将涂布了聚酰胺酸的钛网置于氮气炉中升温,250℃进行闭环缩聚反应8小时,聚酰亚胺的涂层厚度约为200nm,最终在钛网表面进行酰亚胺化而获得聚酰亚胺薄膜,获得的聚酰亚胺/钛网复合材料具有良好的柔性,得到一种柔性聚酰亚胺/钛网复合电极材料。The second step is titanium mesh infiltration and closed-loop polycondensation: cut a specific titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with polyamic acid solution. cloth treatment, and use a scraper to control the coating thickness to 3 μm; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform closed-loop polycondensation at 250°C After 8 hours of reaction, the thickness of the polyimide coating is about 200nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film. The obtained polyimide/titanium mesh composite material has good flexibility. A flexible polyimide/titanium mesh composite electrode material was obtained.
所得的聚酰亚胺/钛网复合电极材料在氧饱和0.1M KOH溶液(pH=13.0)中测量的线性扫描伏安曲线,见图1所示,该电极在1.8V的电压下,电流密度可以达到5mA/cm
2,当电压仅仅增大到1.9V时,电流密度就可增长到15mA/cm
2,并且可以保持较高的电流密度。因此,该电极材料显示了较好的电催化性能。
The linear sweep voltammogram curve of the obtained polyimide/titanium mesh composite electrode material measured in an oxygen-saturated 0.1M KOH solution (pH=13.0) is shown in Figure 1. The electrode has a current density of 1.8V at a voltage of 1.8V. It can reach 5mA/cm 2 . When the voltage only increases to 1.9V, the current density can increase to 15mA/cm 2 and the current density can be maintained at a high level. Therefore, this electrode material shows better electrocatalytic performance.
实施例2Example 2
一种柔性聚酰亚胺碳/钛网复合电极材料,与实施例1步骤近似,按如下步骤制备:A flexible polyimide carbon/titanium mesh composite electrode material is similar to the steps in Example 1 and is prepared as follows:
第一步,聚酰胺酸的制备:The first step is the preparation of polyamic acid:
按照表一的比例投入二胺单体、二酐单体,搅拌溶解在100ml的N,N-二甲基甲酰胺(DMF)中,摩尔浓度(mol%)为:Add diamine monomer and dianhydride monomer according to the proportion in Table 1, stir and dissolve in 100 ml of N,N-dimethylformamide (DMF). The molar concentration (mol%) is:
在黏度达到400泊时结束聚合得到黏度适中的聚酰胺酸;When the viscosity reaches 400 poise, the polymerization is completed to obtain polyamic acid with moderate viscosity;
第二步,钛网浸润与闭环缩聚:将特定的钛网裁剪为5cm*5cm的正方形,采用砂纸打磨以除去表面的氧化层;接着采用浸涂法在钛网表面进行聚酰胺酸溶液的涂布处理,并通过刮刀控制涂覆的厚度在4μm;浸涂处理后放置在100℃的烘箱中干燥,接着将涂布了聚酰胺酸的钛网置于氮气炉中升温,300℃进行闭环缩聚反应8小时,聚酰亚胺的涂层厚度约为300nm,最终在钛网表面进行酰亚胺化而获得聚酰亚胺薄膜,获得的聚酰亚胺/钛网复合材料具有良好的柔性,得到一种柔性聚酰亚胺/钛网复合电极材料,便于加工。The second step is titanium mesh infiltration and closed-loop polycondensation: cut a specific titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with polyamic acid solution. cloth treatment, and use a scraper to control the coating thickness to 4 μm; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform closed-loop polycondensation at 300°C After 8 hours of reaction, the thickness of the polyimide coating is about 300nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film. The obtained polyimide/titanium mesh composite material has good flexibility. A flexible polyimide/titanium mesh composite electrode material is obtained, which is easy to process.
实施例3Example 3
一种柔性聚酰亚胺/钛网薄膜复合电极材料,与实施例1步骤近似,按如下步骤制备:A flexible polyimide/titanium mesh thin film composite electrode material is similar to the steps in Example 1 and is prepared as follows:
第一步,聚酰胺酸的制备:按照表一的比例投入二胺单体、二酐单体,搅拌溶解在100ml的N,N-二甲基甲酰胺(DMF)中,摩尔浓度(mol%)为:The first step is the preparation of polyamic acid: add diamine monomer and dianhydride monomer according to the proportion in Table 1, stir and dissolve in 100 ml of N,N-dimethylformamide (DMF), molar concentration (mol% )for:
在黏度达到400泊时结束聚合得到黏度适中的聚酰胺酸;When the viscosity reaches 400 poise, the polymerization is completed to obtain polyamic acid with moderate viscosity;
第二步,钛网浸润与闭环缩聚:将钛网裁剪为5cm*5cm的正方形,采用砂纸打磨以除去表面的氧化层;接着采用浸涂法在钛网表面进行聚酰胺酸溶液的涂布处理,并通过刮刀控制涂覆的厚度在5μm;浸涂处理后放置在100℃的烘箱中干燥,接着将涂布了聚酰胺酸的钛网置于氮气炉中升温,300℃进行闭环缩聚反应8小时,聚酰亚胺的涂层厚度约为400nm,最终在钛网表面进行酰亚胺化而获得聚酰亚胺薄膜,获得的聚酰亚胺/钛网复合材料具有良好的柔性,得到一种柔性聚酰亚胺/钛网复合电极材料,便于加工。The second step is titanium mesh infiltration and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with a polyamic acid solution. , and control the coating thickness to 5 μm through a scraper; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform a closed-loop polycondensation reaction at 300°C 8 hour, the thickness of the polyimide coating is about 400nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film. The obtained polyimide/titanium mesh composite material has good flexibility and obtains a A flexible polyimide/titanium mesh composite electrode material that is easy to process.
实施例4:Example 4:
一种柔性聚酰亚胺/钛网薄膜复合电极材料,与实施例1步骤近似,按如下步骤制备:A flexible polyimide/titanium mesh thin film composite electrode material is similar to the steps in Example 1 and is prepared as follows:
第一步,聚酰胺酸的制备:按照表一的比例投入二胺单体m-tolidine和BAPP、二酐单体PMDA、BPADA,搅拌溶解在100ml的N,N-二甲基甲酰胺(DMF)中,摩尔浓度(mol%)为:The first step is the preparation of polyamic acid: add diamine monomers m-tolidine and BAPP, dianhydride monomers PMDA and BPADA according to the proportions in Table 1, stir and dissolve in 100ml of N,N-dimethylformamide (DMF ), the molar concentration (mol%) is:
在黏度达到400泊时结束聚合以制备最终的聚酰胺酸;End the polymerization when the viscosity reaches 400 poise to prepare the final polyamic acid;
第二步,钛网浸润与闭环缩聚:将钛网裁剪为5cm*5cm的正方形,采用砂纸打磨以除去表面的氧化层;接着采用浸涂法在钛网表面进行聚酰胺酸溶液的涂布处理,并通过刮刀控制涂覆的厚度在3μm;浸涂处理后放置在100℃的烘箱中干燥,接着将涂布了聚酰胺酸的钛网置于氮气炉中升温,250℃进行闭环缩聚反应8小时,聚酰亚胺的涂层厚度约为300nm,最终在钛网表面进行酰亚胺化而获得聚酰亚胺薄膜,获得的聚酰亚胺/钛网复合材料也具有良好的柔性,得到一种柔性聚酰亚胺/钛网复合电极材料。The second step is titanium mesh infiltration and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square and polish it with sandpaper to remove the oxide layer on the surface; then use dip coating to coat the surface of the titanium mesh with a polyamic acid solution. , and control the coating thickness to 3 μm through a scraper; after dip coating, place it in an oven at 100°C to dry, then place the titanium mesh coated with polyamic acid in a nitrogen furnace to heat up, and perform a closed-loop polycondensation reaction at 250°C 8 hour, the coating thickness of the polyimide is about 300nm. Finally, imidization is performed on the surface of the titanium mesh to obtain a polyimide film. The obtained polyimide/titanium mesh composite material also has good flexibility, and the polyimide film is obtained. A flexible polyimide/titanium mesh composite electrode material.
Claims (10)
- 一种柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法,其特征在于,以钛网为骨架构建的柔性聚酰亚胺/钛网复合电极材料,包括如下步骤:A method for preparing a flexible polyimide/titanium mesh film composite electrode material, which is characterized in that the flexible polyimide/titanium mesh composite electrode material constructed with titanium mesh as a skeleton includes the following steps:第一步,聚酰胺酸的制备:在烧杯里投入二胺单体、二酐单体以及溶剂,进行混合,当溶液的黏度达到350~450泊时,得到的聚酰胺酸溶液即可用于涂覆处理;所述的二酐单体与二胺单体的摩尔比在2:1~1:2,所述的二胺单体,包含由化学式(1)和由化学式(2)表示的二胺单体;所述的化学式(1)、(2)为:The first step is the preparation of polyamic acid: put diamine monomer, dianhydride monomer and solvent into a beaker and mix them. When the viscosity of the solution reaches 350-450 poise, the obtained polyamic acid solution can be used for coating. Coating treatment; the molar ratio of the dianhydride monomer to the diamine monomer is 2:1 to 1:2, and the diamine monomer includes diamine represented by chemical formula (1) and chemical formula (2). Amine monomer; the chemical formulas (1) and (2) are:其中,所述化学式(1)中R 1和R 2分别为C 1-C 6烷基或C 1-C 6烷氧基; Wherein, R 1 and R 2 in the chemical formula (1) are respectively C 1 -C 6 alkyl or C 1 -C 6 alkoxy;所述化学式(2)中R 3为-C(CH 3) 2-、-C(CF 3) 2-、-(CH 2)n 1-、或者-O(CH 2)n 2O-,n 1和n 2分别为1至10的自然数; In the chemical formula (2), R 3 is -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -(CH 2 )n 1 -, or -O(CH 2 )n 2 O-, n 1 and n 2 are natural numbers from 1 to 10 respectively;第二步,浸涂与闭环缩聚:将厚度为0.04~1mm、孔径为0.3~0.5mm的钛网裁剪成5cm*5cm的正方形;将钛网表面氧化层进行打磨处理后,浸入到第一步配置好的聚酰胺酸溶液中,浸渍半小时后取出钛网,刮刀去掉多余的聚酰胺酸树脂,至附着在钛网上的树脂涂层厚度控制在3~5μm,接着,促使涂覆于钛网表面的聚酰胺酸发生闭环缩聚反应,即在钛网表面进行酰亚胺化,得到柔性聚酰亚胺/钛网薄膜复合电极材料。The second step, dip coating and closed-loop polycondensation: cut the titanium mesh with a thickness of 0.04~1mm and aperture of 0.3~0.5mm into a square of 5cm*5cm; after polishing the oxide layer on the surface of the titanium mesh, immerse it into the first step In the prepared polyamic acid solution, take out the titanium mesh after immersing it for half an hour, and remove excess polyamic acid resin with a scraper until the thickness of the resin coating attached to the titanium mesh is controlled to 3 to 5 μm. Then, coat the titanium mesh. The polyamic acid on the surface undergoes a closed-loop polycondensation reaction, that is, imidization is performed on the surface of the titanium mesh to obtain a flexible polyimide/titanium mesh thin film composite electrode material.
- 根据权利要求1所述柔柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法,其特征在于,所述的二酐单体至少为:均苯四甲酸二酐(PMDA)、联苯四甲酸二酐(BPDA)、双酚A型二醚二酐(BPADA)、二苯甲酮四羧酸二酐、氧双邻苯二甲酸酐、以及二苯基砜-3,4,3,4’-四羧酸二中的一种或二种以上的组合;The preparation method of flexible polyimide/titanium mesh thin film composite electrode material according to claim 1, characterized in that the dianhydride monomer is at least: pyromellitic dianhydride (PMDA), biphenyl tetracarboxylic acid Formic dianhydride (BPDA), bisphenol A diether dianhydride (BPADA), benzophenone tetracarboxylic dianhydride, oxybisphthalic anhydride, and diphenyl sulfone-3,4,3,4 '-One or a combination of two or more tetracarboxylic acids;所述的二胺单体至少为:4,4’-二氨基-2,2’-二甲基联苯(m-tolidine)、2,2-双[4-(4-氨基苯氧基)苯基]丙烷(BAPP)、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷(HFBAPP)中的一种或二种以上的组合。The diamine monomer is at least: 4,4'-diamino-2,2'-dimethylbiphenyl (m-tolidine), 2,2-bis[4-(4-aminophenoxy) One or a combination of two or more of phenyl]propane (BAPP) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane (HFBAPP).
- 根据权利要求1或2所述的柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法,其特征在于,第一步中,所述的二酐单体与二胺单体的摩尔比1:1;二胺单体和二酐单体混合产生聚酰胺酸,加入有机极性溶剂N,N-二甲基甲酰胺(DMF)进行混合,在黏度达到350~450泊时,达到涂覆使用要求的聚酰胺酸溶液。The preparation method of flexible polyimide/titanium mesh film composite electrode material according to claim 1 or 2, characterized in that, in the first step, the molar ratio of the dianhydride monomer to the diamine monomer is 1 :1; Diamine monomer and dianhydride monomer are mixed to produce polyamic acid, and the organic polar solvent N,N-dimethylformamide (DMF) is added for mixing. When the viscosity reaches 350 to 450 poise, coating is achieved. Use the required polyamic acid solution.
- 根据权利要求1所述的柔性聚酰亚胺/钛网薄膜复合电极材料的制备方法,其特征在于,第二步中,所述闭环缩聚反应的温度范围为200~400℃,反应时间为8~12h。The method for preparing flexible polyimide/titanium mesh thin film composite electrode material according to claim 1, characterized in that, in the second step, the temperature range of the closed-loop polycondensation reaction is 200-400°C, and the reaction time is 8 ~12h.
- 根据权利要求1至4任一项所述的柔性聚酰亚胺/钛网复合电极材料的制备方法,其特征在于,按如下步骤制备:The method for preparing flexible polyimide/titanium mesh composite electrode material according to any one of claims 1 to 4, characterized in that it is prepared according to the following steps:第一步,聚酰胺酸的制备:将摩尔浓度60%的m-Tolidine和摩尔浓度40%BAPP二胺单体与摩尔浓度60%的BPADA和摩尔浓度40%的PMDA二酐单体,搅拌溶解在100ml的N,N-二甲基甲酰胺(DMF)中,在黏度达到400泊时结束聚合得到黏度适中的聚酰胺酸溶液;The first step is the preparation of polyamic acid: stir and dissolve m-Tolidine with a molar concentration of 60% and BAPP diamine monomer with a molar concentration of 40%, BPADA with a molar concentration of 60% and PMDA dianhydride monomer with a molar concentration of 40%. In 100 ml of N,N-dimethylformamide (DMF), the polymerization is terminated when the viscosity reaches 400 poise to obtain a polyamic acid solution with moderate viscosity;第二步,浸涂与闭环缩聚:将钛网裁剪为5cm*5cm的正方形,用砂纸将钛网表面氧化层进行打磨处理后,浸入到配置好的聚酰胺酸溶液中;浸渍半小时后取出钛网,刮刀去掉多余的聚酰胺酸树脂,控制附着在钛网上的树脂涂层厚度在3μm,涂覆处理后放置在100℃的烘箱中干燥;接着,将涂覆了聚酰胺酸的钛网布置于氮气炉中升温至300℃,进行闭环缩聚反应8小时,至聚酰亚胺的涂层厚度达400nm,得到一种柔性聚酰亚胺/钛网复合电极材料。The second step, dip coating and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square, use sandpaper to polish the oxide layer on the surface of the titanium mesh, and then immerse it in the prepared polyamic acid solution; take it out after half an hour of immersion Titanium mesh, remove excess polyamic acid resin with a scraper, control the thickness of the resin coating attached to the titanium mesh to 3 μm, and place it in an oven at 100°C to dry after coating treatment; then, the titanium mesh coated with polyamic acid Place it in a nitrogen furnace and raise the temperature to 300°C, and perform a closed-loop polycondensation reaction for 8 hours until the thickness of the polyimide coating reaches 400 nm, thereby obtaining a flexible polyimide/titanium mesh composite electrode material.
- 根据权利要求1至4任一项所述的柔性聚酰亚胺/钛网复合电极材料的制备方法,其特征在于,按如下步骤制备:The method for preparing flexible polyimide/titanium mesh composite electrode material according to any one of claims 1 to 4, characterized in that it is prepared according to the following steps:第一步,聚酰胺酸的制备:将摩尔浓度60%的m-Tolidine和摩尔浓度的40%HFBAPP二胺单体与摩尔浓度60%的BPADA和摩尔浓度40%的PMDA的二酐单体,搅拌溶解在100ml的N,N-二甲基甲酰胺DMF中,在黏度达到400泊时,得到黏度适中的聚酰胺酸溶液;The first step is the preparation of polyamic acid: combine 60% molar concentration of m-Tolidine and 40% molar concentration of HFBAPP diamine monomer with 60% molar concentration of BPADA and 40% molar concentration of PMDA dianhydride monomer, Stir and dissolve in 100 ml of N,N-dimethylformamide DMF. When the viscosity reaches 400 poise, a polyamic acid solution with moderate viscosity is obtained;第二步,浸涂与闭环缩聚:将钛网裁剪为5cm*5cm的正方形,用砂纸将钛网表面氧化层进行打磨处理,浸入到配置好的聚酰胺酸溶液中;浸渍半小时后取出钛网,刮刀去掉多余的聚酰胺酸树脂,控制附着在钛网上的树脂涂层厚度在1.6μm;将经过涂覆处理的钛网放置在100℃的烘箱中干燥;接着,布置于氮气炉中升温至300℃,进行闭环缩聚反应8小时;当聚酰亚胺的涂层厚度达到300nm时,得到所述的柔性聚酰亚胺/钛网复合电极材料。The second step, dip coating and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square, use sandpaper to polish the oxide layer on the surface of the titanium mesh, and immerse it in the prepared polyamic acid solution; take out the titanium mesh after half an hour of immersion net, remove excess polyamic acid resin with a scraper, and control the thickness of the resin coating attached to the titanium net to 1.6 μm; place the coated titanium net in an oven at 100°C to dry; then, place it in a nitrogen furnace to heat up to 300°C, and perform a closed-loop polycondensation reaction for 8 hours; when the thickness of the polyimide coating reaches 300 nm, the flexible polyimide/titanium mesh composite electrode material is obtained.
- 根据权利要求1至4任一项所述的柔性聚酰亚胺/钛网复合电极材料的制备方法,其特征在于,按如下步骤制备:The method for preparing flexible polyimide/titanium mesh composite electrode material according to any one of claims 1 to 4, characterized in that it is prepared according to the following steps:第一步,聚酰胺酸的制备:将摩尔浓度70%的m-Tolidine和摩尔浓度30%的HFBAPP二胺单体与摩尔浓度70%m的BPDA和摩尔浓度30%m的PMDA二酐单体,搅拌溶解在100ml的N,N-二甲基甲酰胺(DMF)中,在黏度达到400泊时结束聚合得到黏度适中的聚酰胺酸;The first step is the preparation of polyamic acid: combine 70% molar concentration of m-Tolidine and 30% molar concentration of HFBAPP diamine monomer with 70% molar concentration of BPDA and 30% molar concentration of PMDA dianhydride monomer. , stir and dissolve in 100ml of N,N-dimethylformamide (DMF), and end the polymerization when the viscosity reaches 400 poise to obtain polyamic acid with moderate viscosity;第二步,浸涂与闭环缩聚:将钛网裁剪为5cm*5cm的正方形,用砂纸将钛网表面氧化层进行打磨处理后,浸入到配置好的聚酰胺酸溶液中;浸渍半小时后取出钛网,刮刀去掉多余的聚酰胺酸树脂,控制附着在钛网上的树脂涂层厚度在2μm;随后涂覆了聚酰胺酸的钛网置于100℃的烘箱中干燥,接着,布置于氮气炉中升温至250℃,进行闭环缩聚反应8小时;至聚酰亚胺的涂层厚度为500nm,得到一种柔性聚酰亚胺/钛网复合电极材料。The second step, dip coating and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square, use sandpaper to polish the oxide layer on the surface of the titanium mesh, and then immerse it in the prepared polyamic acid solution; take it out after half an hour of immersion Titanium mesh, remove excess polyamic acid resin with a scraper, and control the thickness of the resin coating attached to the titanium mesh to 2 μm; then the titanium mesh coated with polyamic acid is dried in an oven at 100°C, and then placed in a nitrogen furnace The temperature was raised to 250°C, and a closed-loop polycondensation reaction was carried out for 8 hours; until the thickness of the polyimide coating was 500 nm, a flexible polyimide/titanium mesh composite electrode material was obtained.
- 根据权利要求1至5任一项所述的柔性聚酰亚胺/钛网复合电极材料的制备方法,其特征在于,按如下步骤制备:The method for preparing flexible polyimide/titanium mesh composite electrode material according to any one of claims 1 to 5, characterized in that it is prepared according to the following steps:第一步,聚酰胺酸的制备:将摩尔浓度70%的m-tolidine和摩尔浓度30%的BAPP二胺单体与摩尔浓度70%的BPDA和摩尔浓度30%的BPADA二酐单体,搅拌溶解在100ml的N,N-二甲基甲酰胺(DMF)中,在黏度达到400泊时结束聚合,制备得到聚酰胺酸溶液;The first step is the preparation of polyamic acid: stir the m-tolidine with a molar concentration of 70% and the BAPP diamine monomer with a molar concentration of 30% with the BPDA with a molar concentration of 70% and the BPADA dianhydride monomer with a molar concentration of 30%. Dissolve in 100 ml of N,N-dimethylformamide (DMF), end the polymerization when the viscosity reaches 400 poise, and prepare a polyamic acid solution;第二步,浸涂与闭环缩聚:将钛网裁剪为5cm*5cm的正方形,用砂纸将钛网表面氧化层进行打磨处理后,浸入到配置好的聚酰胺酸溶液中;浸渍半小时后取出钛网,刮刀去掉多余的聚酰胺酸树脂,控制附着在钛网上的树脂涂层厚度在3μm;随后,放置在100℃的烘箱中干燥后,将涂覆了聚酰胺酸的钛网布置于氮气炉中升温,250℃进行闭环缩聚反应8小时,聚酰亚胺的涂层厚度达 600nm时,得到柔性聚酰亚胺/钛网复合电极材料。The second step, dip coating and closed-loop polycondensation: cut the titanium mesh into a 5cm*5cm square, use sandpaper to polish the oxide layer on the surface of the titanium mesh, and then immerse it in the prepared polyamic acid solution; take it out after half an hour of immersion Titanium mesh, remove excess polyamic acid resin with a scraper, and control the thickness of the resin coating attached to the titanium mesh to 3 μm; then, after drying in an oven at 100°C, place the titanium mesh coated with polyamic acid in nitrogen. The temperature is raised in the furnace and a closed-loop polycondensation reaction is carried out at 250°C for 8 hours. When the thickness of the polyimide coating reaches 600nm, a flexible polyimide/titanium mesh composite electrode material is obtained.
- 一种柔性聚酰亚胺/钛网薄膜复合电极材料,其特征在于,根据权利要求1-8任一所述方法制备得到的。A flexible polyimide/titanium mesh thin film composite electrode material, characterized in that it is prepared according to the method of any one of claims 1-8.
- 根据权利要求9所述柔性聚酰亚胺/钛网薄膜复合电极材料在电催化中的应用。The application of the flexible polyimide/titanium mesh film composite electrode material in electrocatalysis according to claim 9.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011124360A (en) * | 2009-12-10 | 2011-06-23 | Fujifilm Corp | Thin-film transistor and method for manufacturing the same, and device including the same |
CN104103812A (en) * | 2014-07-21 | 2014-10-15 | 国家纳米科学中心 | Composite flexible electrode material as well as preparation method and application thereof |
CN106350835A (en) * | 2016-08-30 | 2017-01-25 | 中信大锰矿业有限责任公司 | Manufacture method of rare earth anode plate in electrolytic manganese electrolysis process |
CN110054262A (en) * | 2019-05-27 | 2019-07-26 | 安徽工业大学 | A kind of ternary modified titanium-matrix electrode, preparation method and application |
CN113737213A (en) * | 2021-09-01 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of flexible polyimide carbon cloth composite electrode material, product and application thereof |
CN115323420A (en) * | 2022-08-04 | 2022-11-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of flexible polyimide/titanium mesh film composite electrode material, product and application thereof |
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- 2022-12-16 WO PCT/CN2022/139572 patent/WO2024027076A1/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011124360A (en) * | 2009-12-10 | 2011-06-23 | Fujifilm Corp | Thin-film transistor and method for manufacturing the same, and device including the same |
CN104103812A (en) * | 2014-07-21 | 2014-10-15 | 国家纳米科学中心 | Composite flexible electrode material as well as preparation method and application thereof |
CN106350835A (en) * | 2016-08-30 | 2017-01-25 | 中信大锰矿业有限责任公司 | Manufacture method of rare earth anode plate in electrolytic manganese electrolysis process |
CN110054262A (en) * | 2019-05-27 | 2019-07-26 | 安徽工业大学 | A kind of ternary modified titanium-matrix electrode, preparation method and application |
CN113737213A (en) * | 2021-09-01 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of flexible polyimide carbon cloth composite electrode material, product and application thereof |
CN115323420A (en) * | 2022-08-04 | 2022-11-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of flexible polyimide/titanium mesh film composite electrode material, product and application thereof |
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