CN105047955A - Preparation method of carbon paper coating for fuel cell based on layer-by-layer self-assembly technique - Google Patents
Preparation method of carbon paper coating for fuel cell based on layer-by-layer self-assembly technique Download PDFInfo
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- CN105047955A CN105047955A CN201510283165.9A CN201510283165A CN105047955A CN 105047955 A CN105047955 A CN 105047955A CN 201510283165 A CN201510283165 A CN 201510283165A CN 105047955 A CN105047955 A CN 105047955A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- 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
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
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- Fuel Cell (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method of a carbon paper coating for a fuel cell based on a layer-by-layer self-assembly technique. The preparation method comprises the following steps: (1), carrying out surface treatment on carbon paper by a plasma grafting apparatus, and forming negative electricity on the surface of the carbon paper; (2), immersing the treated carbon paper base into a branched polyethylenimine (bPEI) water solution for 1-15 minutes, and taking out and flushing the carbon paper base with distilled water; and (3), immersing the carbon paper base treated in the step (2) into a polyacrylic acid (PAA) water solution for 1-15 minutes, taking out and flushing the carbon paper base with the distilled water, repeating the steps (2) and (3), and repeatedly assembling multi-layer polyelectrolyte on the surface of the carbon paper base, so as to obtain the carbon paper protection coating with the self-repairing capability. According to the preparation method, the carbon paper protection coating with the self-repairing capability can be conveniently prepared at low cost; the carbon paper coating can be used as a protection layer for the carbon paper; the oxidation degree of the carbon paper is retarded in the use procedure; the service life of the carbon paper is prolonged; and the cycling stability of the fuel cell is improved.
Description
Technical field
The present invention relates to a kind of preparation method of the fuel cell carbon paper protective finish based on laminated assembling technology; the blended coating of this multi-layer polyelectrolyte can not only protect carbon paper; slow down and be in use oxidized extent of exfoliation; the water produced in fuel cell operations can also be utilized after damaged to repair fast; thus the useful life of the prolongation battery of high degree; improve the cycle performance of battery, belong to energy environment technical field.
Background technology
Carbon paper is also called carbon fiber paper (cloth), it is the proprietary material of fuel cell experiment, as gas diffusion layers main material, play conduction electron, gas passage is provided and discharges the multiple actions such as water, it is one of critical component affecting battery electrode performance, but it is easy to oxidized and layering in the course of the work, even peels off, and has a strong impact on useful life and the cyclical stability of fuel cell.
The principle of self-repair material mimic biology bulk damage healing, at Materials Fracture or when being subject to machinery scraping, the reparation mainly realized for damage by inherent resource itself.Selfreparing both can spontaneously after material is damaged be carried out, and also can bring out self-repair procedure by the environmental stimuli such as light, heat.
Layer-by-layer (Layer-by-Layerselfassembly) is the method preparing order thin film that development in recent years is got up.It utilizes the Electrostatic Absorption characteristic of organic or inorganic zwitterion, forms film by the alternately molecule deposition of counter ion system.The people such as D.Decher in 1991 have carried out pionerring research with adsorption technology layer by layer to structure order thin film.They prepare multilayer film with amphipathic organic cation-anion (or polyelectrolyte) at ionization substrate surface alternating sorbent.Up to the present, a variety of materials such as carbon nano-tube, protein, nucleic acid, phosphatide and organic/inorganic particle all are successfully used for there is specific composition, the multilayer order film of thickness and character.First Lyon and South point out, hydrogel thin film prepared by LBL self-assembly can heal fast under water is the condition of initator.We based on LBL self-assembly method, have constructed branched polyethylene base imines (bPEI)/polyacrylic acid (PAA)-graphene oxide (GO) the layer assembly polyelectrolyte film with scratch removal ability in the course of work in early stage.
The fuel cell carbon paper protective finish prepared based on layer assembly heals fast under the condition being initator with water.Its principle is: after the protective finish with self-reparing capability is impaired; the water produced when running into hydrogen fuel cell work; can absorbing water fast, it is swelling to occur; thus cause the coating of damaged part to be displaced sideways, the polyelectrolyte of impaired oppositely charged is contacted with each other and again forms electrostatical binding and repair damage.
At this in the works, we are by laminated assembling technology, gather acetimide and polyacrylic acid, prepare the carbon paper protective finish with self-reparing capability, controllable thickness, size and surface texture in carbon paper substrate cocycle deposition branching.
Summary of the invention
Technical problem: the preparation method that the object of this invention is to provide a kind of fuel cell carbon paper protective finish based on layer-by-layer, the polyelectrolyte blend film that this law is constructed not only effectively will protect carbon paper, weaken carbon paper oxidation in the course of the work and extent of exfoliation, but also self-reparing capability fast will be had, can self-regeneration rapidly after impaired, extend the useful life of carbon paper, improve the cyclical stability of fuel cell, this just needs the pH value to strictly controlling poly-electrolyte in an assembling process; Because the polyelectrolyte blend film conductivity of constructing is poor, so thickness also will strictly control.
Technical scheme: concrete technical scheme of the present invention is as follows:
The present invention makes public for the first time a kind of preparation method of the fuel cell carbon paper coating based on layer-by-layer; with the carbon paper after surface treatment for substrate; for raw material, the carbon paper protective finish with self-reparing capability is prepared by layer-by-layer with the polyelectrolyte of oppositely charged (branching gathers acetimide (bPEI) and polyacrylic acid (PAA)).
The preparation method of the fuel cell carbon paper coating based on layer-by-layer of the present invention comprises the following steps:
Step one, carries out surface treatment by carbon paper plasma grafting instrument, makes its surface band negative electricity, as the base material of postorder assembling;
Step 2, the carbon paper substrate after process immerses branching and gathers 1-30 minutes rear distilled water flushings of taking-up in the acetimide bPEI aqueous solution;
Step 3, to immerse the carbon paper substrate through step 2 process in the polyacrylic acid PAA aqueous solution 1-30 minutes, takes out rear distilled water flushing;
Repeat step 2 and step 3, repeatedly at facial mask substrate surface assembling multi-layer polyelectrolyte, thus obtain the carbon paper protective finish with self-reparing capability.
The carbon paper protective finish prepared of described layer-by-layer raw material used is: branching gathers acetimide/polyacrylic acid, also can gather acetimide/hyaluronic acid, shitosan/polyacrylic acid or shitosan/sodium alginate by branching and substitute.
Beneficial effect: the fuel cell carbon paper protective finish that the present invention utilizes branching to gather acetimide/polyacrylic acid to be prepared by Electrostatic Absorption; in the present invention; we pass through laminated assembling technology; gather acetimide and polyacrylic acid in carbon paper substrate cocycle deposition branching, prepare the carbon paper protective finish with self-reparing capability, controllable thickness, size and surface texture.
Have the following advantages:
1. based on the fuel cell carbon paper protective finish that layer-by-layer is prepared; the oxidation be subject in the carbon paper course of work and corrosiveness can not only be slowed down; also there is self-reparing capability fast; even if also can repair rapidly after impaired; extend the useful life of carbon paper, improve the cycle performance of fuel cell.
2. method is simply effective, easy and simple to handle, and required time is shorter, and preparation facilities is simple, and do not need special equipment, common culture dish, pH meter and drying box just can meet the demands.
3. applied range: the protective finish constructed by LBL self-assembly method can be applied on fuel cell carbon paper incessantly; can also with similar material for substrate; assembling coating; thus have certain protective effect to substrate, on the metal even can assembled thus for corrosion of metal protection aspect.
4. nontoxic: the material selected is all bio-compatible or degradable, thus to environment all green have, be extraordinary ecological environment material nd.
Accompanying drawing explanation
Fig. 1 be fuel cell carbon paper coating impaired after self-repair procedure figure.
Fig. 2 is fuel cell carbon paper coating (L: the different number of plies) and the electrolysis figure of conventional carbon paper in water.
Embodiment
Preparation method based on the fuel cell carbon paper coating based on layer-by-layer of the present invention comprises the following steps:
Step one, carries out surface treatment by carbon paper plasma grafting instrument, makes its surface band negative electricity;
Step 2, the carbon paper substrate after process is immersed in branching and gathers in acetimide (bPEI) aqueous solution 1-30 minutes, takes out rear distilled water flushing;
Step 3, to be dipped in polyacrylic acid (PAA) aqueous solution 1-30 minutes, to take out rear distilled water flushing by the carbon paper substrate through step 2 process;
Repeat step 2 and step 3, repeatedly at facial mask substrate surface assembling multi-layer polyelectrolyte, thus obtain the carbon paper protective finish with self-reparing capability.
Described carbon paper protective finish can by the polyelectrolyte of number of different types (such as: branching gathers acetimide/polyacrylic acid; Branching gathers acetimide/hyaluronic acid; Shitosan/polyacrylic acid and shitosan/sodium alginate etc.) preparation.
Described carbon paper substrate is the general carbon paper material of fuel cell.
The built-up time of described step 2 and step 3, for different experimental situations and technique, can fluctuate up and down.
Set forth the present invention further below in conjunction with specific embodiment, but not limit the scope of the invention.
Embodiment 1
Step one, carries out surface treatment by carbon paper plasma grafting instrument, makes its surface band negative electricity;
Step 2, the carbon paper substrate after process is immersed in branching and gathers in acetimide (bPEI) aqueous solution 30 minutes, takes out rear distilled water flushing;
Step 3, to be dipped in hyaluronic acid (HA) aqueous solution 15 minutes, to take out rear distilled water flushing by the carbon paper substrate through step 2 process;
Repeat step 2 and step 3, repeatedly at facial mask substrate surface assembling multi-layer polyelectrolyte, thus obtain the carbon paper protective finish with self-reparing capability.
Embodiment 2
Step one, carries out surface treatment by carbon paper plasma grafting instrument, makes its surface band negative electricity;
Step 2, the carbon paper substrate after process to be immersed in shitosan (chitosan) aqueous solution 15 minutes, takes out rear distilled water flushing;
Step 3, to be dipped in polyacrylic acid (PAA) aqueous solution 30 minutes, to take out rear distilled water flushing by the carbon paper substrate through step 2 process;
Repeat step 2 and step 3, repeatedly at facial mask substrate surface assembling multi-layer polyelectrolyte, thus obtain the carbon paper protective finish with self-reparing capability.
Embodiment 3
Step one, carries out surface treatment by carbon paper plasma grafting instrument, makes its surface band negative electricity;
Step 2, the carbon paper substrate after process to be immersed in shitosan (chitosan) aqueous solution 5 minutes, takes out rear distilled water flushing;
Step 3, to be dipped in sodium alginate (NaAlg) aqueous solution 5 minutes, to take out rear distilled water flushing by the carbon paper substrate through step 2 process;
Repeat step 2 and step 3, repeatedly at facial mask substrate surface assembling multi-layer polyelectrolyte, thus obtain the carbon paper protective finish with self-reparing capability.
Claims (1)
1., based on a fuel cell preparation method for carbon paper coating for layer-by-layer, it is characterized in that the method comprises the following steps:
Step one, carries out surface treatment by carbon paper plasma grafting instrument, makes its surface band negative electricity, as the base material of postorder assembling;
Step 2, the carbon paper substrate after process immerses branching and gathers 1-30 minutes rear distilled water flushings of taking-up in the acetimide bPEI aqueous solution;
Step 3, to immerse the carbon paper substrate through step 2 process in the polyacrylic acid PAA aqueous solution 1-30 minutes, takes out rear distilled water flushing;
Repeat step 2 and step 3, repeatedly at facial mask substrate surface assembling multi-layer polyelectrolyte, thus obtain the carbon paper protective finish with self-reparing capability.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105623475A (en) * | 2016-03-31 | 2016-06-01 | 青岛农业大学 | Method for preparing self-healing coating based on environment-friendly nanometer container |
| CN109411808A (en) * | 2017-08-18 | 2019-03-01 | 通用汽车环球科技运作有限责任公司 | Selfreparing gel-type electrolyte composite material |
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| CN101924220A (en) * | 2010-08-27 | 2010-12-22 | 东南大学 | Modification method for electrode of microbial fuel cell |
| CN103556543A (en) * | 2013-10-24 | 2014-02-05 | 浙江科技学院 | Special high-performance carbon paper for gas diffusion layer of fuel cell and preparation method of carbon paper |
| CN104257510A (en) * | 2014-08-28 | 2015-01-07 | 东南大学 | Preparation method of functional nano-microcapsule mask based on layer-by-layer self assembly |
| CN104261392A (en) * | 2014-09-22 | 2015-01-07 | 东南大学 | Preparation method of borate ion crosslinked conductive graphene paper |
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- 2015-05-28 CN CN201510283165.9A patent/CN105047955A/en active Pending
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| CN101924220A (en) * | 2010-08-27 | 2010-12-22 | 东南大学 | Modification method for electrode of microbial fuel cell |
| CN103556543A (en) * | 2013-10-24 | 2014-02-05 | 浙江科技学院 | Special high-performance carbon paper for gas diffusion layer of fuel cell and preparation method of carbon paper |
| CN104257510A (en) * | 2014-08-28 | 2015-01-07 | 东南大学 | Preparation method of functional nano-microcapsule mask based on layer-by-layer self assembly |
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| CN105623475A (en) * | 2016-03-31 | 2016-06-01 | 青岛农业大学 | Method for preparing self-healing coating based on environment-friendly nanometer container |
| CN105623475B (en) * | 2016-03-31 | 2018-06-01 | 青岛农业大学 | A kind of preparation method of the self-healing coating based on environmentally friendly nano container |
| CN109411808A (en) * | 2017-08-18 | 2019-03-01 | 通用汽车环球科技运作有限责任公司 | Selfreparing gel-type electrolyte composite material |
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