CN107317043B - Preparation method of graphene/tin dioxide sandwich structure film on surface of aluminum alloy bipolar plate - Google Patents
Preparation method of graphene/tin dioxide sandwich structure film on surface of aluminum alloy bipolar plate Download PDFInfo
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention relates to a preparation method of a graphene/tin dioxide sandwich structure film on the surface of an aluminum alloy bipolar plate, which comprises the following steps: (1) mixing deionized water with absolute ethyl alcohol, adding stannous chloride dihydrate, and adjusting the pH to 9-10 to obtain a hydrothermal precursor solution; (2) placing the pretreated aluminum alloy bipolar plate in NaOH solution, performing chemical etching, cleaning and drying; (3) the aluminum alloy bipolar plate after chemical etching is recycled in PDDA aqueous solution and graphene oxide aqueous solution for one or more times of circulating self-assembly, and is taken out, cleaned and dried; (4) and (3) placing the aluminum alloy bipolar plate subjected to self-assembly in the step (3) in the hydrothermal precursor solution prepared in the step (1), carrying out hydrothermal reaction, cleaning and drying to obtain the aluminum alloy bipolar plate. Compared with the prior art, the invention has the advantages of simple operation, low cost, good corrosion resistance effect and the like.
Description
Technical Field
The invention relates to the technical field of proton exchange membrane fuel cells, in particular to a preparation method of a graphene/tin dioxide sandwich structure film on the surface of an aluminum alloy bipolar plate.
Background
With the continuous development and progress of society, the problems of energy exhaustion, environmental pollution and the like also come with the society. The severity of a series of problems due to human development is increasingly recognized today in the 21 st century. Nowadays, the reserves of petrochemical energy are getting smaller and smaller, and the development of renewable clean pollution-free energy has attracted worldwide attention, and fuel cells are one of the intelligent crystals of human beings. The proton exchange membrane fuel cell (PEMFC, also called polymer electrolyte membrane fuel cell) is the latest generation of fuel cell, mainly utilizes the chemical energy generated by the reaction of hydrogen and oxygen to convert into electric energy, discharges only water vapor and does not contain greenhouse gases such as carbon dioxide and the like, and has the advantages of high efficiency, energy conservation, environmental protection, quick start, low working temperature (60-80 ℃) and the like. The bipolar plate, which is an important component of PEMFC, not only occupies 70 to 80% of the total mass of the stack and almost the entire volume, but also occupies a considerable proportion in the production cost of the stack, so it is very important to select the material of the bipolar plate.
The bipolar plate materials mainly used at present are: graphite, composite materials, metallic materials. Compared with other bipolar plate materials, the metal material has the characteristics of good thermal conductivity, strong electrical conductivity, high mechanical strength, good processability, low cost and the like, and has attracted wide attention. Aluminum and its alloys can also be used as a bipolar plate material of PEMFCs in terms of their electrical conductivity, mechanical strength, density, etc. due to their large reserves. Meanwhile, the application is limited due to the defects that the active surface is easy to passivate and is easy to corrode due to chemical properties. In order to make it widely available, it has become a necessary task to modify its surface to improve its electrical conductivity and corrosion resistance.
In recent years, there have been many studies on the modification of the material of the bipolar plate of the proton exchange membrane fuel cell, but these methods generally have the disadvantages of complicated treatment process, high cost, poor stability, and the like. Chinese patent No. 200810202639.2 discloses a surface modification method for metal bipolar plate of proton exchange membrane fuel cell in the energy technology field, the bipolar plate is composed of surface modification layer and base stainless steel, copper ions are injected into stainless steel thin plate by ion injection method, injection layer is formed in the range of tens nanometers on the surface of stainless steel thin plate, and modified stainless steel bipolar plate is obtained. The corrosion resistance of the stainless steel modified by the method is not greatly improved, and the corrosion current density of the bare stainless steel is 11.76 muA cm-2The corrosion current density after modification is only 7 muA cm-2The corrosion inhibition efficiency is only 40.48%, and the preparation conditions of the method are very harsh, and the method needs extremely high voltage and high temperature.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a graphene/tin dioxide sandwich structure film on the surface of an aluminum alloy bipolar plate.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a graphene/tin dioxide sandwich structure film on the surface of an aluminum alloy bipolar plate comprises the following steps:
(1) mixing deionized water with absolute ethyl alcohol, adding stannous chloride dihydrate, and adjusting the pH to 9-10 to obtain a hydrothermal precursor solution;
(2) placing the pretreated aluminum alloy bipolar plate in NaOH solution, performing chemical etching, cleaning and drying;
(3) the aluminum alloy bipolar plate after chemical etching is recycled in PDDA aqueous solution and graphene oxide aqueous solution for one or more times of circulating self-assembly, and is taken out, cleaned and dried;
(4) and (3) placing the aluminum alloy bipolar plate after the self-assembly in the step (3) in the hydrothermal precursor solution prepared in the step (1), carrying out hydrothermal reaction, cleaning and drying to obtain the graphene/stannic oxide sandwich structure film on the surface of the aluminum alloy bipolar plate.
Preferably, the ratio of the added amounts of the deionized water, the absolute ethyl alcohol and the stannous chloride dihydrate in the step (1) is 20-40 mL: 10mL of: 0.1-0.3 g.
Preferably, the solution used to adjust the pH in step (1) is a 1M NaOH solution.
Preferably, the concentration of the NaOH solution in the step (2) is 0.8-1.2M, and the process conditions of the chemical etching are as follows: etching at 50-70 deg.C for 20-40 s.
Preferably, in the step (2), the pretreatment specifically comprises:
polishing the aluminum alloy bipolar plate, placing the aluminum alloy bipolar plate in acetone for ultrasonic cleaning, and then sequentially washing the aluminum alloy bipolar plate with absolute ethyl alcohol and deionized water to remove oil stains and grease on the surface of the aluminum alloy.
More preferably, the grinding treatment comprises the following specific steps: the sand paper is sequentially polished by water grinding sand paper of 600#, 1000#, 1500# and 2000#, and then polished by metallographic sand paper of W3.5.
Preferably, in the step (3), the self-assembly process conditions in the PDDA aqueous solution are as follows: self-assembling for 8-15min in PDDA aqueous solution with volume fraction of 0.8-1.2%;
the process conditions of self-assembly in the graphene oxide aqueous solution are as follows: self-assembling for 8-15min in graphene oxide aqueous solution with the mass fraction of 0.8-1.2 wt%.
Preferably, the number of the cyclic assembly of step (3) is 10.
Preferably, the conditions of the hydrothermal reaction in the step (4) are as follows: carrying out hydrothermal reaction at 110-130 ℃ for 4-8 h.
Preferably, in the step (4), the conditions for washing and drying after the hydrothermal reaction are as follows: after washing, drying overnight at 60 ℃.
The mechanism of adopting NaOH solution chemical etching in the invention is as follows:
2Al+2NaOH+6H2O→2Na[Al(OH)4]+3H2↑
in the hydrothermal reaction process, reducing graphene oxide into reduced graphene oxide with excellent performance by adopting a thermal reduction method; the mechanism of tin dioxide generation is:
the surface of the graphene/tin dioxide sandwich structure film prepared by the method is in a simulated liquid (0.5M H) for simulating a proton exchange membrane fuel cell2SO4+2ppm HF), after the film layer is stabilized, the corrosion potential is shifted by 496mV, and the corrosion current density reaches 3.457 multiplied by 10-7A·cm-2And the corrosion inhibition rate can reach 99.59 percent, and the corrosion inhibitor shows very good corrosion resistance.
According to the method, the NaOH solution is used as the etching liquid to etch the surface of the aluminum alloy, so that hydroxyl is obtained on the surface of the aluminum alloy. The aqueous solution of PDDA has positive charges and can be combined with the surface of hydroxylated aluminum alloy through electrostatic attraction. The aqueous solution of the graphene oxide has negative charges and can be combined with the PDDA modified surface with positive charges through electrostatic attraction. And (3) performing self-assembly for 10 times in a circulating way in the aqueous solution of the PDDA and the graphene oxide respectively to obtain the graphene oxide layer. And carrying out hydrothermal treatment, wherein the graphene oxide is thermally reduced to form reduced graphene oxide, and stannous chloride in water is converted into stannic oxide with excellent stability, so that the surface of the graphene/stannic oxide sandwich structure film is prepared. The method has the advantages of simple operation, low cost, good corrosion resistance effect and the like. The graphene/tin dioxide sandwich structure film finally obtained by the preparation method has higher corrosion resistance on the surface.
Compared with the prior art, the invention has the following advantages:
1) and (3) obtaining a PDDA/graphene oxide modified surface on the surface of the aluminum alloy by adopting a self-assembly method, and finally obtaining reduced graphene oxide through thermal reduction.
2) A method combining a self-assembly method and a hydrothermal method is adopted to prepare a surface film with a sandwich structure on the surface of aluminum alloy, and the research on enhancing the corrosion resistance of the aluminum alloy material in the PEMFC environment belongs to innovation
3) The preparation process is simple, the conditions are mild, the cost is low, the stability is high, the environment is protected, the prepared graphene/tin dioxide sandwich structure film surface has the corrosion inhibition efficiency of 99.59 percent, and the corrosion resistance is excellent.
Drawings
FIG. 1 shows aluminum alloys at 0.5M H for various treated surfaces2SO4Potentiodynamic polarization curve plot in simulated fluid of +2ppm HF;
FIG. 2 shows an aluminum alloy at 0.5M H for various treated surfaces2SO4A list of relevant chemical parameters corresponding to a potentiodynamic polarization curve graph in simulated fluid of +2ppm HF;
FIG. 3 is a surface topography of a blank aluminum alloy at 1000 magnifications;
FIG. 4 is a surface topography of an aluminum alloy etched with NaOH solution at 1000 magnification;
FIG. 5 is a surface topography of pure graphene oxide at 4000-magnification;
FIG. 6 is a surface topography of pure tin dioxide at 5000 magnifications;
fig. 7 is a surface topography of the graphene/tin dioxide sandwich structure thin film under a magnification of 5000.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
The method for determining the surface morphology characterization of the graphene/tin dioxide sandwich structure thin film on the surface of the aluminum alloy with the corrosion resistance provided by the invention uses a scanning electron microscope (SU-1500, Hitachi, Japan) to observe the surface morphology of a sample.
Electrochemical analysis
The alternating current impedance test and the measurement of the polarization curve are completed in a three-electrode system, a working electrode is an aluminum alloy electrode with a constructed graphene/tin dioxide sandwich structure film, and an auxiliary electrode and a reference electrode are a Pt electrode and a Saturated Calomel Electrode (SCE) respectively. The electrochemical test employed an instrument, Chenghua CHI660E electrochemical workstation. The impedance frequency range is 100kHz-0.05Hz, and the peak value of the alternating current excitation signal is 5 mV; the polarization curve scan range E + -200 mV (vs. SCE) with a scan rate of 1 mV/s.
The corrosion inhibition efficiency (η%) was calculated according to the following equation:
wherein I0And I is the corrosion current density of the untreated and treated aluminum alloy electrodes, respectively.
Example 1
A preparation method of a graphene/tin dioxide sandwich structure film on the surface of an aluminum alloy bipolar plate comprises the following steps:
(1) preparation of etching solution
Preparing a NaOH solution with the concentration of 1M as an etching solution;
(2) preparation of aqueous PDDA solution
Preparing a PDDA aqueous solution with the volume ratio of 1% for self-assembly;
(3) preparation of graphene oxide aqueous solution
Preparing a graphene oxide aqueous solution with the mass fraction of 1 wt% for self-assembly;
(4) preparation of hydrothermal precursor solution
According to the volume ratio of deionized water to absolute ethyl alcohol of 3: 1, respectively mixing 30mL of deionized water and 10mL of absolute ethanol, adding 0.15g of stannous chloride dihydrate, uniformly mixing, and adjusting the pH value of the solution to 9-10 by using 1M NaOH;
(5) pretreatment of aluminum alloy
5 pieces (1, 2, 3, 4 and 5) of aluminum alloy are sequentially polished by water-grinding abrasive paper of 600#, 1000#, 1500# and 2000#, and then by the metallographic abrasive paper of W3.5. Cleaning the substrate in acetone solution for about 15min, and sequentially washing the substrate with absolute ethyl alcohol and deionized water to remove surface oil stains and grease;
(6) chemical etching
Taking out 4 pieces (2, 3, 4 and 5) of aluminum alloy pretreated in the step (5), immersing the aluminum alloy into the etching solution obtained in the step (1), etching for 30s under the condition of 60 ℃ in a water bath, and ultrasonically cleaning for 5min by using deionized water and ethanol respectively after etching;
(7) self-assembly process
And (3) respectively putting 2 aluminum alloys (3 and 5) obtained after etching in the step (6) into the solutions prepared in the steps (2) and (3) for soaking for 10min, and circulating for 10 times for self-assembly.
(8) Hydrothermal treatment
Putting 1 aluminum alloy (5) obtained after the PDDA/graphene oxide obtained in the step (7) is modified and 1 aluminum alloy (4) obtained after the step (6) is etched into a reaction kettle, adding 10mL of the precursor solution prepared in the step (4), and carrying out hydrothermal reaction at 120 ℃ for 6 hours; and (3) putting 1 piece of the modified PDDA/graphene oxide obtained in the step (7) into a reaction kettle, adding 10mL of deionized water, and carrying out hydrothermal reaction at 120 ℃ for 6 hours.
FIG. 1 and FIG. 2 show the bare aluminum alloy (1) obtained by the above steps, the aluminum alloy (2) obtained by etching, the pure graphene film modified aluminum alloy (3), the pure tin dioxide film modified aluminum alloy (4) and graphite respectivelyThe alkene/stannic oxide sandwich structure thin film modified aluminum alloy (5) is 0.5M H2SO4Potentiodynamic polarization curve diagram and alternating current impedance diagram obtained by testing in proton exchange membrane fuel cell simulation liquid of +2ppm HF. Table 1 is a list of the relevant chemical parameters in fig. 1, and it is known from table 1 that the corrosion current densities of the bare aluminum alloy (1), the aluminum alloy (2) obtained after etching, the pure graphene film modified aluminum alloy (3), the pure tin dioxide film modified aluminum alloy (4), and the graphene/tin dioxide sandwich structure thin film modified aluminum alloy (5) are 8.356 × 10-5A/cm2、2.161×10-5A/cm2、4.924×10-6A/cm2、2.851×10-6A/cm2、3.457×10-7A/cm2The corrosion potential is respectively as follows: -710mV, -521mV, -419mV, -406mV, -234 mV. Compared with bare aluminum alloy, the graphene/tin dioxide sandwich structure film modified aluminum alloy has the advantages that the corrosion potential is shifted by 496mV positively, and the corrosion inhibition efficiency is as high as 99.59%. As shown in fig. 2, the resistance value of the graphene/tin dioxide sandwich structure thin film modified aluminum alloy is the largest, which corresponds to the best corrosion resistance.
FIG. 3 is a 1000-magnification blank aluminum alloy surface topography with uniform scratches on the surface. FIG. 4 is a surface topography of an aluminum alloy etched with NaOH solution at 1000 times, wherein the surface of the etched aluminum alloy has a cell-like morphology and hydroxyl groups are obtained on the surface. Fig. 5 is a surface topography of pure graphene oxide at a magnification of 4000, the topography has a typical feature of a wrinkled shape of graphene oxide, and graphene can be used for corrosion prevention, so that the surface of the aluminum alloy can be protected to a certain extent. FIG. 6 is a surface topography of pure tin dioxide under 5000 multiplying power, the diameter of the spherical assembled topography is about 1-2 μm, the spherical assembled topography is uniformly covered on the surface of the aluminum alloy, meanwhile, the aluminum alloy can be well protected from corrosion due to the excellent stability of tin dioxide, FIG. 7 is a surface topography of a graphene/tin dioxide sandwich structure film under 5000 multiplying power, the composited topography is changed slightly compared with the surface topography of the pure tin dioxide, but the lamellar structure of the small spheres is thinner, and the composite structure and the graphene have the combined effect, so that the protection effect on the aluminum alloy substrate is achieved.
Example 2:
the preparation method of the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate specifically comprises the following steps:
(1) preparation of etching solution
Preparing a NaOH solution with the concentration of 1M as an etching solution;
(2) preparation of aqueous PDDA solution
Preparing a PDDA aqueous solution with the volume ratio of 1% for self-assembly;
(3) preparation of graphene oxide aqueous solution
Preparing a graphene oxide aqueous solution with the mass fraction of 1 wt% for self-assembly;
(4) preparation of hydrothermal precursor solution
According to the volume ratio of deionized water to absolute ethyl alcohol of 1: 3, respectively mixing 10mL of deionized water and 30mL of absolute ethanol, adding 0.15g of stannous chloride dihydrate, uniformly mixing, and adjusting the pH value of the solution to 9-10 by using 1M NaOH;
(5) pretreatment of aluminum alloy
The aluminum alloy is sequentially polished by water-milled sand paper of 600#, 1000#, 1500# and 2000#, and then polished by metallographic sand paper of W3.5. Cleaning the substrate in acetone solution for about 15min, and sequentially washing the substrate with absolute ethyl alcohol and deionized water to remove surface oil stains and grease;
(6) chemical etching
Taking out the aluminum alloy pretreated in the step (5), immersing the aluminum alloy into the etching solution obtained in the step (1), etching for 30s under the condition of water bath at 60 ℃, and respectively ultrasonically cleaning for 5min by using deionized water and ethanol after etching;
(7) self-assembly process
And (3) respectively putting the aluminum alloy obtained after etching in the step (6) into the solutions prepared in the steps (2) and (3) for soaking for 10min, and circulating for 10 times for self-assembly.
(8) Hydrothermal treatment
And (3) putting the PDDA/graphene oxide modified aluminum alloy obtained in the step (7) into a reaction kettle, adding 10mL of the precursor solution prepared in the step (4), and carrying out hydrothermal reaction at 120 ℃ for 6 hours to obtain the surface of the film with the graphene/tin dioxide sandwich structure.
Example 3:
the preparation method of the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate specifically comprises the following steps:
(1) preparation of etching solution
Preparing a NaOH solution with the concentration of 1M as an etching solution;
(2) preparation of aqueous PDDA solution
Preparing a PDDA aqueous solution with the volume ratio of 1% for self-assembly;
(3) preparation of graphene oxide aqueous solution
Preparing a graphene oxide aqueous solution with the mass fraction of 1 wt% for self-assembly;
(4) preparation of hydrothermal precursor solution
According to the volume ratio of deionized water to absolute ethyl alcohol of 3: 1, respectively mixing 30mL of deionized water and 10mL of absolute ethanol, adding 0.15g of stannous chloride dihydrate, uniformly mixing, and adjusting the pH value of the solution to 9-10 by using 1M NaOH;
(5) pretreatment of aluminum alloy
The aluminum alloy is sequentially polished by water-milled sand paper of 600#, 1000#, 1500# and 2000#, and then polished by metallographic sand paper of W3.5. Cleaning the substrate in acetone solution for about 15min, and sequentially washing the substrate with absolute ethyl alcohol and deionized water to remove surface oil stains and grease;
(6) chemical etching
Taking out the aluminum alloy pretreated in the step (5), immersing the aluminum alloy into the etching solution obtained in the step (1), etching for 30s under the condition of water bath at 60 ℃, and respectively ultrasonically cleaning for 5min by using deionized water and ethanol after etching;
(7) self-assembly process
And (4) respectively putting the aluminum alloy obtained after etching in the step (6) into the solutions prepared in the steps (2) and (3) for soaking for 10min, and circulating for 5 times for self-assembly.
(8) Hydrothermal treatment
And (3) putting the PDDA/graphene oxide modified aluminum alloy obtained in the step (7) into a reaction kettle, adding 10mL of the precursor solution prepared in the step (4), and carrying out hydrothermal reaction at 120 ℃ for 6 hours to obtain the surface of the film with the graphene/tin dioxide sandwich structure.
Example 4:
the preparation method of the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate specifically comprises the following steps:
(1) preparation of etching solution
Preparing a NaOH solution with the concentration of 1M as an etching solution;
(2) preparation of aqueous PDDA solution
Preparing a PDDA aqueous solution with the volume ratio of 1% for self-assembly;
(3) preparation of graphene oxide aqueous solution
Preparing a graphene oxide aqueous solution with the mass fraction of 1 wt% for self-assembly;
(4) preparation of hydrothermal precursor solution
According to the volume ratio of deionized water to absolute ethyl alcohol of 3: 1, respectively mixing 30mL of deionized water and 10mL of absolute ethanol, adding 0.15g of stannous chloride dihydrate, uniformly mixing, and adjusting the pH value of the solution to 9-10 by using 1M NaOH;
(5) pretreatment of aluminum alloy
The aluminum alloy is sequentially polished by water-milled sand paper of 600#, 1000#, 1500# and 2000#, and then polished by metallographic sand paper of W3.5. Cleaning the substrate in acetone solution for about 15min, and sequentially washing the substrate with absolute ethyl alcohol and deionized water to remove surface oil stains and grease;
(6) chemical etching
Taking out the aluminum alloy pretreated in the step (5), immersing the aluminum alloy into the etching solution obtained in the step (1), etching for 30s under the condition of water bath at 60 ℃, and respectively ultrasonically cleaning for 5min by using deionized water and ethanol after etching;
(7) self-assembly process
And (3) respectively putting the aluminum alloy obtained after etching in the step (6) into the solutions prepared in the steps (2) and (3) for soaking for 10min, and circulating for 10 times for self-assembly.
(8) Hydrothermal treatment
And (3) putting the PDDA/graphene oxide modified aluminum alloy obtained in the step (7) into a reaction kettle, adding 10mL of the precursor solution prepared in the step (4), and carrying out hydrothermal reaction at 150 ℃ for 6 hours to obtain the surface of the film with the graphene/tin dioxide sandwich structure.
Example 5
The preparation method of the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate specifically comprises the following steps:
(1) preparation of etching solution
Preparing a NaOH solution with the concentration of 0.8M as an etching solution;
(2) preparation of aqueous PDDA solution
Preparing a PDDA aqueous solution with the volume ratio of 0.8% for self-assembly;
(3) preparation of graphene oxide aqueous solution
Preparing a graphene oxide aqueous solution with the mass fraction of 0.8 wt% for self-assembly;
(4) preparation of hydrothermal precursor solution
According to the volume ratio of deionized water to absolute ethyl alcohol of 2: 1, respectively mixing 20mL of deionized water and 10mL of absolute ethyl alcohol, then adding 0.1g of stannous chloride dihydrate, uniformly mixing, and adjusting the pH value of the solution to 9-10 by using 1M NaOH;
(5) pretreatment of aluminum alloy
The aluminum alloy is sequentially polished by water-milled sand paper of 600#, 1000#, 1500# and 2000#, and then polished by metallographic sand paper of W3.5. Cleaning the substrate in acetone solution for about 15min, and sequentially washing the substrate with absolute ethyl alcohol and deionized water to remove surface oil stains and grease;
(6) chemical etching
Taking out the aluminum alloy pretreated in the step (5), immersing the aluminum alloy into the etching solution obtained in the step (1), etching for 40s under the condition of water bath at 50 ℃, and respectively ultrasonically cleaning for 5min by using deionized water and ethanol after etching;
(7) self-assembly process
And (4) respectively putting the aluminum alloy obtained after etching in the step (6) into the solutions prepared in the steps (2) and (3) for soaking for 8min, and performing cycle circulation for 10 times of self-assembly.
(8) Hydrothermal treatment
And (3) putting the PDDA/graphene oxide modified aluminum alloy obtained in the step (7) into a reaction kettle, adding 10mL of the precursor solution prepared in the step (4), and carrying out hydrothermal reaction at 110 ℃ for 8h to obtain the surface of the film with the graphene/tin dioxide sandwich structure.
Example 6
The preparation method of the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate specifically comprises the following steps:
(1) preparation of etching solution
Preparing a NaOH solution with the concentration of 1.2M as an etching solution;
(2) preparation of aqueous PDDA solution
Preparing a PDDA aqueous solution with the volume ratio of 1.2% for self-assembly;
(3) preparation of graphene oxide aqueous solution
Preparing a graphene oxide aqueous solution with the mass fraction of 1.2 wt% for self-assembly;
(4) preparation of hydrothermal precursor solution
According to the volume ratio of deionized water to absolute ethyl alcohol of 4: 1, respectively mixing 40mL of deionized water and 10mL of absolute ethyl alcohol, then adding 0.3g of stannous chloride dihydrate, uniformly mixing, and adjusting the pH value of the solution to 9-10 by using 1M NaOH;
(5) pretreatment of aluminum alloy
The aluminum alloy is sequentially polished by water-milled sand paper of 600#, 1000#, 1500# and 2000#, and then polished by metallographic sand paper of W3.5. Cleaning the substrate in acetone solution for about 15min, and sequentially washing the substrate with absolute ethyl alcohol and deionized water to remove surface oil stains and grease;
(6) chemical etching
Taking out the aluminum alloy pretreated in the step (5), immersing the aluminum alloy into the etching solution obtained in the step (1), etching for 20s under the condition of water bath at 70 ℃, and respectively ultrasonically cleaning for 5min by using deionized water and ethanol after etching;
(7) self-assembly process
And (3) respectively putting the aluminum alloy obtained after etching in the step (6) into the solutions prepared in the steps (2) and (3) for soaking for 15min, and circulating for 10 times for self-assembly.
(8) Hydrothermal treatment
And (3) putting the PDDA/graphene oxide modified aluminum alloy obtained in the step (7) into a reaction kettle, adding 10mL of the precursor solution prepared in the step (4), and carrying out hydrothermal reaction at 130 ℃ for 4h to obtain the surface of the film with the graphene/tin dioxide sandwich structure.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A preparation method of a graphene/tin dioxide sandwich structure film on the surface of an aluminum alloy bipolar plate is characterized by comprising the following steps:
(1) mixing deionized water with absolute ethyl alcohol, adding stannous chloride dihydrate, and adjusting the pH to 9-10 to obtain a hydrothermal precursor solution;
(2) placing the pretreated aluminum alloy bipolar plate in NaOH solution, performing chemical etching, cleaning and drying;
(3) the aluminum alloy bipolar plate after chemical etching is recycled in PDDA aqueous solution and graphene oxide aqueous solution for one or more times of circulating self-assembly, and is taken out, cleaned and dried;
(4) placing the aluminum alloy bipolar plate subjected to self-assembly in the step (3) in the hydrothermal precursor solution prepared in the step (1), carrying out hydrothermal reaction, cleaning and drying to obtain a graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate;
in the step (3), the self-assembly process conditions in the PDDA aqueous solution are as follows: self-assembling for 8-15min in PDDA aqueous solution with volume fraction of 0.8-1.2%;
the process conditions of self-assembly in the graphene oxide aqueous solution are as follows: self-assembling for 8-15min in graphene oxide aqueous solution with the mass fraction of 0.8-1.2 wt%;
the conditions of the hydrothermal reaction in the step (4) are as follows: carrying out hydrothermal reaction at 110-130 ℃ for 4-8 h;
the adding amount ratio of the deionized water, the absolute ethyl alcohol and the stannous chloride dihydrate in the step (1) is 20-40 mL: 10mL of: 0.1-0.3 g.
2. The method for preparing the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate according to claim 1, wherein the solution used for adjusting the pH in the step (1) is a 1M NaOH solution.
3. The method for preparing the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate according to claim 1, wherein the concentration of NaOH solution in the step (2) is 0.8-1.2M, and the chemical etching process conditions are as follows: etching at 50-70 deg.C for 20-40 s.
4. The method for preparing the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate according to claim 1, wherein in the step (2), the pretreatment specifically comprises the following steps:
polishing the aluminum alloy bipolar plate, placing the aluminum alloy bipolar plate in acetone for ultrasonic cleaning, and then sequentially washing the aluminum alloy bipolar plate with absolute ethyl alcohol and deionized water to remove oil stains and grease on the surface of the aluminum alloy.
5. The method for preparing the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate according to claim 4, wherein the polishing treatment comprises the following specific steps: the sand paper is sequentially polished by water grinding sand paper of 600#, 1000#, 1500# and 2000#, and then polished by metallographic sand paper of W3.5.
6. The method for preparing the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate according to claim 1, wherein the number of times of cyclic assembly in the step (3) is 10.
7. The method for preparing the graphene/tin dioxide sandwich structure film on the surface of the aluminum alloy bipolar plate according to claim 1, wherein in the step (4), the conditions of cleaning and drying after the hydrothermal reaction are as follows: after washing, drying overnight at 60 ℃.
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