CN115458785B - Preparation method of direct methanol fuel cell sol-gel electrolyte - Google Patents

Preparation method of direct methanol fuel cell sol-gel electrolyte Download PDF

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CN115458785B
CN115458785B CN202211193653.7A CN202211193653A CN115458785B CN 115458785 B CN115458785 B CN 115458785B CN 202211193653 A CN202211193653 A CN 202211193653A CN 115458785 B CN115458785 B CN 115458785B
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methanol
sol
sulfuric acid
gel electrolyte
acid solution
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CN115458785A (en
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鞠剑峰
丁欣宇
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Nantong University
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • H01M8/1074—Sol-gel processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • 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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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Composite Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Fuel Cell (AREA)

Abstract

The invention relates to the technical field of new energy, in particular to a preparation method of a direct methanol fuel cell sol-gel electrolyte, which is formed by wrapping methanol and sulfuric acid solution by taking polyvinyl alcohol-polyaniline PVA-PANI as a framework. The sol-gel electrolyte prepared by the invention has higher proton conductivity, higher methanol leakage prevention performance, better flexibility and mechanical property, controllable shape, capability of reducing the poisoning of a methanol catalyst, improving the performance of a direct methanol fuel cell and reducing the manufacturing cost of the DMFC.

Description

Preparation method of direct methanol fuel cell sol-gel electrolyte
Technical Field
The invention relates to the technical field of new energy, in particular to a preparation method of a direct methanol fuel cell sol-gel electrolyte.
Background
The ever-increasing energy demand brings about the problems of environmental pollution and exhaustion of the traditional energy fast consumption, and the finding of new energy which has high energy utilization efficiency, is environment-friendly and can be continuously developed is of great importance. The fuel cell is a device for converting chemical energy into electric energy, has higher efficiency and less pollution, is the most promising power generation technology, and is expected to solve the energy problem. Among them, the direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) has the advantages of low energy consumption, high energy density, rich methanol source, low price, simple system, convenient operation, low noise, etc., and is considered as the most promising chemical power source for future automobile power and other vehicles, and is attracting attention. One of the key problems faced in the development of DMFC is that the solid electrolyte membrane widely used in the current direct methanol fuel cell is a Nafion membrane originally designed for use in oxyhydrogen proton exchange membrane fuel cells, and has a remarkable phenomenon of methanol leakage (cross over), and in addition, due to the liquid encapsulation of methanol electrolyte, CO generated by anodic methanol oxidation 2 Mass transfer is limited and also results in increased methanol leakage. The leaked methanol penetrates through the Nafion membrane to reach the cathode, so that not only is the methanol fuel largely lost, but also mixed potential is formed at the cathode, the performance of the DMFC is greatly reduced, the service life of the DMFC is shortened, and the manufacturing cost of the direct methanol fuel cell is increased.
The current research can be divided into two aspects, namely, modifying Nafion membrane, such as adding inorganic matters into the gaps or surfaces of Nafion membrane as methanol leakage barrier layer, such as zeolite molecular sieve, pd and TiO 2 、SiO 2 And the like, can reduce methanol leakage by more than 50 percent, or research Nafion composite membranes, synthesize a plurality of novel proton exchange membranes with low methanol transmittance and high proton conductivity, such as polymer membranes containing phosphotungstic acid, sulfonated membranes and the like, and change the DMFC structureThe selectivity of hydrogen proton mass transfer in methanol and electrolyte is improved, a methanol mass transfer barrier layer is increased, the methanol mass transfer resistance is improved, and CO is effectively migrated 2 Reducing methanol leakage (e.g., (1) Xuejin Sun et al Molecular sieve as an effective barrier for methanol crossover in direct methanol fuel cells, international Journal of Hydrogen Energy,2020,45 (15): 8994-9003. (2) W.J.Chen, W.Yuan, G.Z.Ye, F.C.Han, Y.Tang, utilization and positive effects of produced CO) 2 on the performance of a passive direct methanol fuel cell with a composite anode structure, international Journal of Hydrogen Energy,2017, 42:15613-15622). Although the methanol leakage is greatly reduced, the methanol leakage problem is not solved. From the DMFC electrolyte itself, solid-phase direct methanol fuel cell electrolytes have been developed in japan, but mass transfer is limited. CN200710020181.4 reports the formation of SiO with sodium silicate or ethyl silicate as precursors 2 The sol-gel mobile phase electrolyte is a framework, which reduces the leakage of methanol by more than 90% compared with the liquid phase methanol electrolyte, and SiO 2 The conductivity of the sol-gel electrolyte is poor, the proton conductivity of the sol-gel electrolyte is not ideal, and the shape of the sol-gel electrolyte is difficult to control when the sol-gel electrolyte is added into a DMFC.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation method of a direct methanol fuel cell sol-gel electrolyte, which not only solves the problem of methanol leakage, but also greatly improves the proton conducting capacity of the direct methanol fuel cell sol-gel electrolyte, has good flexibility and mechanical property, can control the shape of the direct methanol fuel cell sol-gel electrolyte, can reduce the toxicity of a methanol catalyst, improves the performance of a DMFC, can reduce the manufacturing cost of the DMFC, and promotes the commercial application process of the DMFC.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the sol-gel electrolyte of the direct methanol fuel cell comprises the steps of:
s1, callTaking a certain amount of polyvinyl alcohol PVA, adding a certain amount of H with the concentration of 1-4mol/L 2 SO 4 Magnetically stirring for 30 minutes at normal temperature, heating to 90 ℃, and stirring and dissolving at a speed of 80 revolutions per minute;
s2, adding a certain amount of methanol into the solution obtained in the step S1 after cooling, slowly stirring at a speed of 60-80 rpm, and continuing stirring after sol is formed to form gel with PVA as a framework and wrapping methanol and sulfuric acid solution;
s3, weighing a certain amount of aniline, and adding a certain amount of H with the concentration of 1-4mol/L 2 SO 4 Adding the mixture into the gel prepared in the step S2 after stirring and dissolving, and standing for 4 hours;
s4, weighing ammonium persulfate as an initiator according to the molar ratio of the ammonium persulfate to the aniline of 1:1, and using a certain amount of H with the concentration of 1-2mol/L 2 SO 4 Dissolving to form sulfuric acid solution of ammonium persulfate;
and S5, dropwise adding the ammonium persulfate solution obtained in the step S4 into the product obtained in the step S3, cooling to 0-4 ℃, sealing, and stirring for reacting for 4 hours to obtain the direct methanol fuel cell sol-gel electrolyte with the polyvinyl alcohol-polyaniline PVA-PANI as a framework, wherein the framework is internally wrapped with methanol and sulfuric acid solution.
Preferably, the mass fraction of PVA in the PVA-PANI skeleton is 25-40%, and the mass fraction of PANI in the PVA-PANI skeleton is 60-75%.
Preferably, the concentration of methanol in the solution of methanol and sulfuric acid which are wrapped by PVA-PANI skeleton in the sol-gel electrolyte is 0.5-4mol/L, H 2 SO 4 The concentration is 0.5-2mol/L.
Compared with the prior art, the invention has the following beneficial effects:
1. the PVA-PANI skeleton has higher conductivity, and the sol-gel electrolyte has higher proton conductivity, thereby being beneficial to improving the performance of the direct methanol fuel cell.
2. The sol-gel electrolyte prepared by the invention has higher methanol leakage resistance, better flexibility and mechanical property and controllable shape; can reduce the poisoning of the methanol catalyst, improve the performance of the DMFC, reduce the manufacturing cost of the DMFC and promote the commercial application process of the DMFC.
Drawings
FIG. 1 is a scanning electron microscope image of a sol-gel electrolyte with PVA-PANI as a framework in the invention;
FIG. 2 is a graph of methanol leakage concentration versus time for the sol gel electrolyte and the liquid electrolyte of example 1 of the present invention; wherein, (a) is the sol-gel electrolyte in example 1, and (b) is the liquid-phase electrolyte.
Detailed Description
The following technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the protection scope of the present invention is more clearly defined. The described embodiments of the present invention are intended to be only a few, but not all embodiments of the present invention, and all other embodiments that may be made by one of ordinary skill in the art without inventive faculty are intended to be within the scope of the present invention.
Example 1:
s1, weighing 5g of PVA (molecular weight 1799), adding 40mL of H with the concentration of 1mol/L 2 SO 4 Magnetically stirring for 30 min at normal temperature, heating to 90 ℃, and stirring at a speed of 80 rpm for dissolution;
s2, adding 4.6mL of methanol after cooling, continuously stirring to form sol slowly, and finally forming gel, and sealing after the gel is formed in the preparation process;
s3, weighing 9.36 g of aniline, and adding 30mL of H with the concentration of 2mol/L 2 SO 4 Adding the mixture into the gel prepared in the step S2 after stirring and dissolving, and standing for 4 hours;
s4, weighing 22.8g of ammonium persulfate initiator, and using 30mL of H with concentration of 1mol/L 2 SO 4 Dissolving to form sulfuric acid solution of ammonium persulfate;
s5, dropwise adding the ammonium persulfate solution obtained in the step S4 into the product obtained in the step S2, sealing at 0-4 ℃, and stirring for reacting for 4 hours to obtain the direct methanol fuel cell sol-gel electrolyte with 35% PVA mass fraction and 65% PANI mass fraction as a framework, wherein 1mol/L methanol and 1.1mol/L sulfuric acid solution are enclosed in the framework.
Example 2:
s1, weighing 6.3g PVA (molecular weight 1799), adding 40mL H with concentration of 2mol/L 2 SO 4 Magnetically stirring for 30 min at normal temperature, heating to 90 ℃, and stirring at a speed of 80 rpm for dissolution;
s2, adding 9.2mL of methanol after cooling, continuously stirring to form sol slowly, and finally forming gel, and sealing after the gel is formed in the preparation process;
s3, weighing 9.36 g of aniline, and adding 30mL of H with the concentration of 2mol/L 2 SO 4 Adding the mixture into the gel prepared in the step S2 after stirring and dissolving, and standing for 4 hours;
s4, weighing 22.8g of ammonium persulfate initiator, and using 30mL of H with concentration of 2mol/L 2 SO 4 Dissolving to form sulfuric acid solution of ammonium persulfate;
s5, dropwise adding the ammonium persulfate solution obtained in the step S4 into the product obtained in the step S2, sealing at 0-4 ℃, and stirring for reacting for 4 hours to obtain the direct methanol fuel cell sol-gel electrolyte with the PVA mass fraction of 40% and the PANI mass fraction of 60% serving as a framework, wherein 2mol/L methanol and 1.6mol/L sulfuric acid solution are enclosed in the framework.
Example 3:
s1, 8.1g of PVA (molecular weight 1799) is weighed and 40mL of H with the concentration of 1mol/L is added 2 SO 4 Magnetically stirring for 30 min at normal temperature, heating to 90 ℃, and stirring at a speed of 80 rpm for dissolution;
s2, adding 9.2mL of methanol after cooling, continuously stirring to form sol slowly, and finally forming gel, and sealing after the gel is formed in the preparation process;
s3, weighing 18.7 g of aniline, and adding 30mL of H with the concentration of 1mol/L 2 SO 4 Adding the mixture into the gel prepared in the step S2 after stirring and dissolving, and standing for 4 hours;
s4, weighing 45.6g of ammonium persulfate initiator, and using 30mL of H with concentration of 1mol/L 2 SO 4 Dissolving to form sulfuric acid solution of ammonium persulfate;
s5, dropwise adding the ammonium persulfate solution obtained in the step S4 into the product obtained in the step S2, sealing at 0-4 ℃, and stirring for reacting for 4 hours to obtain the direct methanol fuel cell sol-gel electrolyte with the PVA mass fraction of 30% and the PANI mass fraction of 70% serving as a framework, wherein 1.5mol/L methanol and 0.8mol/L sulfuric acid solution are enclosed in the framework.
Referring to proton exchange membrane conductivity measurement methods, the conductivities of the sol-gel electrolytes in example 1, example 2, and example 3 and the liquid phase electrolytes at the same sulfuric acid and methanol concentrations were measured, respectively, and the results are shown in table 1.
The calculation formula is as follows:
wherein, sigma: conductivity, R: measuring resistance, S: area, L: thickness.
Table 1 conductivity test results
The results in Table 1 show that the PVA-PANI skeleton sol-gel electrolyte has higher conductivity than the liquid electrolyte.
The sol-gel electrolyte taking PVA-PANI as a framework is dehydrated by gradient ethanol, freeze-dried by methanol and tert-butanol, then subjected to vacuum platinization, and the morphology of the electrolyte is observed by adopting a scanning electron microscope, and the result is shown in figure 1.
As can be seen from fig. 1, the sol-gel electrolyte with PVA-PANI as a skeleton has an obvious pore structure, and the skeleton is a PVA-PANI copolymer with a cross-linked structure, which has better flexibility and mechanical properties, is beneficial to adjusting the properties of the electrolyte in a DMFC, and can adjust the pore size and the methanol mass transfer rate by adjusting the content of each component in the sol-gel electrolyte with PVA-PANI as a skeleton, thereby solving the methanol leakage problem and improving the battery performance.
Determination of PVA-PANI skeleton solution by diaphragm diffusion Chi FaLeakage performance of the gel electrolyte. The diffusion pool is composed of two half chambers, one half chamber is added with sol-gel electrolyte taking PVA-PANI as a framework, and the other half chamber is added with deionized water. The Nafion 117 membrane is sandwiched between two half chambers and is filled with 70% sulfuric acid and 30% H before use 2 O 2 Soaking for 24 hours. Samples were taken once an hour and the methanol concentration in the deionized water side chamber was measured by a gas chromatograph.
Example 1 the methanol leakage concentration versus time for a sol gel electrolyte and a liquid electrolyte at the same sulfuric acid and methanol concentrations is shown in fig. 2.
FIG. 2 shows that methanol leakage concentration is linear with time.
Slope of straight line:
the permeability coefficient P of methanol is determined from the slope of the straight line:
wherein: v (V) B The deionized water side chamber volume was 100mL, and the membrane area A was 4.09cm 2 L is film thickness, C A Is the methanol concentration.
FIG. 2 shows that the slope of the methanol leakage concentration-time curve of the sol gel electrolyte of example 1 is much smaller than that of the methanol leakage concentration-time curve of the liquid phase electrolyte, and the permeation coefficients are 6.35×10 respectively -8 cm 2 S -1 And 1.41×10 - 6 cm 2 S -1 The embodiment 1 shows that the methanol leakage of the sol-gel electrolyte is reduced by more than 95% compared with that of the liquid electrolyte, and the sol-gel electrolyte has better methanol leakage prevention performance.
The description and practice of the invention disclosed herein will be readily apparent to those skilled in the art, and may be modified and adapted in several ways without departing from the principles of the invention. Accordingly, modifications or improvements may be made without departing from the spirit of the invention and are also to be considered within the scope of the invention.

Claims (3)

1. The preparation method of the sol-gel electrolyte of the direct methanol fuel cell is characterized in that the sol-gel electrolyte is formed by wrapping methanol and sulfuric acid solution by taking polyvinyl alcohol-polyaniline as a framework, and the preparation method comprises the following steps:
s1, weighing a certain amount of polyvinyl alcohol, adding a certain amount of sulfuric acid solution with the concentration of 1-4mol/L, magnetically stirring for 30 minutes at normal temperature, heating to 90 ℃, and stirring and dissolving at the speed of 80 revolutions per minute;
s2, adding a certain amount of methanol into the solution obtained in the step S1 after cooling, slowly stirring at a speed of 60-80 rpm, and continuing stirring after sol is formed to form gel with polyvinyl alcohol as a framework and wrapping methanol and sulfuric acid solution;
s3, weighing a certain amount of aniline, adding the aniline into a certain amount of sulfuric acid solution with the concentration of 1-4mol/L, stirring and dissolving the aniline, adding the aniline into the gel prepared in the step S2, and standing the gel for 4 hours;
s4, weighing ammonium persulfate as an initiator according to a molar ratio of the ammonium persulfate to the aniline of 1:1, and dissolving the ammonium persulfate with a certain amount of sulfuric acid solution with the concentration of 1-2mol/L to form a sulfuric acid solution of ammonium persulfate;
s5, dropwise adding the sulfuric acid solution of the ammonium persulfate in the step S4 into the product of the step S3, cooling to 0-4 ℃, sealing, and stirring for reacting for 4 hours to obtain the direct methanol fuel cell sol-gel electrolyte with the polyvinyl alcohol-polyaniline as a framework, wherein the framework is internally wrapped with methanol and sulfuric acid solution.
2. The method for preparing the direct methanol fuel cell sol-gel electrolyte according to claim 1, wherein in the step S5, the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol-polyaniline skeleton is 25-40%, and the mass fraction of the polyaniline in the polyvinyl alcohol-polyaniline skeleton is 60-75%.
3. The method for preparing a sol-gel electrolyte for a direct methanol fuel cell according to claim 1, wherein in the step S5, the concentration of methanol is 0.5-4mol/L and the concentration of sulfuric acid solution is 0.5-2mol/L in a solution of methanol and sulfuric acid which are included in a polyvinyl alcohol-polyaniline skeleton in the sol-gel electrolyte.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101047262A (en) * 2007-03-02 2007-10-03 南通大学 Sol-gel mobile phase of direct methanol fuel cell and preparation method
CN101093892A (en) * 2007-07-11 2007-12-26 南通大学 Membrane mobile phase of direct methanol fuel cell, and preparation method
JP2009224133A (en) * 2008-03-14 2009-10-01 Jsr Corp Polymer electrolyte for direct methanol fuel cell, and its usage
CN112151817A (en) * 2020-10-26 2020-12-29 中北大学 Copper-based anode catalyst for direct methanol fuel cell and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101047262A (en) * 2007-03-02 2007-10-03 南通大学 Sol-gel mobile phase of direct methanol fuel cell and preparation method
CN101093892A (en) * 2007-07-11 2007-12-26 南通大学 Membrane mobile phase of direct methanol fuel cell, and preparation method
JP2009224133A (en) * 2008-03-14 2009-10-01 Jsr Corp Polymer electrolyte for direct methanol fuel cell, and its usage
CN112151817A (en) * 2020-10-26 2020-12-29 中北大学 Copper-based anode catalyst for direct methanol fuel cell and preparation method thereof

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