CN115458785A - Preparation method of sol-gel electrolyte of direct methanol fuel cell - Google Patents

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

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CN115458785A
CN115458785A CN202211193653.7A CN202211193653A CN115458785A CN 115458785 A CN115458785 A CN 115458785A CN 202211193653 A CN202211193653 A CN 202211193653A CN 115458785 A CN115458785 A CN 115458785A
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gel electrolyte
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鞠剑峰
丁欣宇
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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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Abstract

The invention relates to the technical field of new energy, in particular to a preparation method of a sol-gel electrolyte of a direct methanol fuel cell. The sol-gel electrolyte prepared by the invention has higher proton conductivity, higher methanol leakage resistance, better flexibility and mechanical property and controllable shape, can reduce the poisoning of a methanol catalyst, improve the performance of a direct methanol fuel cell and reduce the manufacturing cost of DMFC.

Description

Preparation method of sol-gel electrolyte of direct methanol fuel cell
Technical Field
The invention relates to the technical field of new energy, in particular to a preparation method of a sol-gel electrolyte of a direct methanol fuel cell.
Background
The problem of environmental pollution and the problem of exhaustion of traditional energy sources due to the ever-increasing energy demand are brought, and the finding of new energy sources which are high in energy utilization efficiency, friendly to the environment and capable of being developed sustainably is very important. 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 can be expected to solve the energy problem. Among them, the Direct Methanol Fuel Cell (DMFC) has the advantages of low energy consumption, high energy density, abundant Methanol sources, low price, simple system, convenient operation, low noise, etc., and is considered to be the most promising chemical power source for future automobile power and other vehicles, and attracts people's wide attention. One of the key issues facing the development of DMFC is the current direct methanol fuel cellThe widely adopted solid electrolyte membrane is a Nafion membrane originally designed for a hydrogen-oxygen proton exchange membrane fuel cell, has obvious methanol leakage (crossover) phenomenon, and in addition, because of liquid encapsulation of a methanol electrolyte, CO generated by anode methanol oxidation 2 Also leads to increased methanol leakage. The leaked methanol penetrates the Nafion membrane to reach the cathode, so that not only is a large amount of methanol fuel 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 improved.
The current research can be roughly divided into two aspects, namely, the modification of the Nafion membrane, such as the doping of inorganic substances in the gaps or on the surface of the Nafion membrane as a methanol leakage barrier layer, such as zeolite molecular sieve, pd and TiO 2 、SiO 2 The methanol leakage can be reduced by more than 50 percent, or Nafion composite membrane is researched to synthesize some novel proton exchange membranes with low methanol transmittance and high proton conductivity, such as phosphotungstic acid-containing polymer membrane, sulfonated membrane and the like, and the DMFC structure is changed to improve the selectivity of hydrogen proton mass transfer in methanol and electrolyte, increase a methanol mass transfer barrier layer, improve the methanol mass transfer resistance and effectively migrate CO 2 Reduce methanol leakage (e.g., (1) Xuejing Sun et al, molecular single as an effective barrier for methanol cross in direct methanol fuels, international Journal of Hydrogen Energy,2020,45 (15): 8994-9003. (2) W.J.Chen, W.Yuan, G.Z.Ye, F.C.Han, Y.Tang, ultilization and reactive 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. Although the methanol leakage is greatly reduced, the problem of methanol leakage is not solved. Starting from the DMFC electrolyte itself, japan developed and studied solid phase direct methanol fuel cell electrolytes, but mass transfer was limited. CN200710020181.4 reports that sodium silicate or ethyl silicate is taken as precursor to form SiO 2 The seepage of the skeleton sol-gel mobile phase electrolyte to methanol is reduced by more than 90 percent compared with the liquid phase methanol electrolyte, and in addition, siO 2 The sol is not conductive per se, and the sol is coagulatedThe proton conductivity of the gel electrolyte is not ideal, and the shape is difficult to control when the gel electrolyte is added into the DMFC.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a preparation method of a sol-gel electrolyte of a direct methanol fuel cell, which not only solves the problem of methanol leakage, but also greatly improves the proton conducting capacity of the electrolyte, and the electrolyte has better flexibility and mechanical property, can control the shape of the electrolyte, can reduce the toxicity of a methanol catalyst, improves the performance of DMFC, can also reduce the manufacturing cost of the DMFC, and promotes the commercial application process of the DMFC.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing sol-gel electrolyte of a direct methanol fuel cell is disclosed, wherein the sol-gel electrolyte is prepared by wrapping methanol and sulfuric acid solution by using polyvinyl alcohol-polyaniline PVA-PANI as a framework, and the preparation method comprises the following steps:
s1, weighing a certain amount of polyvinyl alcohol PVA, and 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 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 the speed of 60-80 revolutions per minute, and continuously stirring after sol is formed to form gel with PVA as a framework 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 After stirring and dissolving, adding the gel prepared in the step S2, and standing for 4 hours;
s4, weighing ammonium persulfate as an initiator according to the molar ratio of 1 2 SO 4 Dissolving to form a 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 and the methanol and sulfuric acid solution wrapped in the framework.
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, in the solution of methanol and sulfuric acid wrapped by the PVA-PANI skeleton in the sol-gel electrolyte, the concentration of the methanol is 0.5-4mol/L, and the concentration of 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 invention forms semisolid sol-gel electrolyte taking PVA-PANI copolymer as a framework, the PVA-PANI framework has higher conductivity, and the sol-gel electrolyte has higher proton conductivity, thereby being beneficial to improving the performance of a direct methanol fuel cell.
2. The sol-gel electrolyte prepared by the invention has higher methanol leakage resistance, better flexibility and mechanical property, and can control the shape of the electrolyte; can reduce the toxicity 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 skeleton according to the present invention;
FIG. 2 is a graph of methanol leakage concentration versus time for a sol-gel electrolyte and a liquid phase electrolyte in example 1 of the present invention; wherein (a) is the sol-gel electrolyte of example 1, and (b) is a liquid-phase electrolyte.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below 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 scope of the present invention is more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art based on the embodiments described herein are intended to be within the scope of the present invention.
Example 1:
s1, weighing 5g of PVA (molecular weight 1799), and adding 40mL of H with the concentration of 1mol/L 2 SO 4 Magnetically stirring for 30 minutes at normal temperature, heating to 90 ℃, and stirring at the speed of 80 r/min for dissolving;
s2, cooling, adding 4.6mL of methanol, continuously stirring to slowly form sol, finally forming gel, and sealing in the preparation process and after the gel is formed;
s3, weighing 9.36 g of aniline, and adding 30mL of 2mol/L H 2 SO 4 After stirring and dissolving, adding the gel prepared in the step S2, and standing for 4 hours;
s4, weighing 22.8g of ammonium persulfate initiator and using 30mL of H with the concentration of 1mol/L 2 SO 4 Dissolving to form a 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 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 35% and the PANI mass fraction of 65% as a framework, wherein 1mol/L methanol and 1.1mol/L sulfuric acid solution are encapsulated in the framework.
Example 2:
s1, 6.3g of PVA (molecular weight 1799) is weighed, 40mL of H with the concentration of 2mol/L is added 2 SO 4 Magnetically stirring for 30 minutes at normal temperature, heating to 90 ℃, and stirring at the speed of 80 r/min for dissolving;
s2, cooling, adding 9.2mL of methanol, continuously stirring to slowly form sol, finally forming gel, and sealing in the preparation process and after the gel is formed;
s3, weighing 9.36 g of aniline, and adding 30mL of 2mol/L H 2 SO 4 After stirring and dissolving, adding the gel prepared in the step S2, and standing for 4 hours;
s4, weighing 22.8g of ammonium persulfate initiator, and adding 30mL of H with the concentration of 2mol/L 2 SO 4 Dissolving to form a 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 S2, sealing at 0-4 ℃, and stirring for reaction 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% as a framework, wherein 2mol/L methanol and 1.6mol/L sulfuric acid solution are encapsulated in the framework.
Example 3:
s1, weighing 8.1g of PVA (molecular weight 1799), and adding 40mL of 1mol/L H 2 SO 4 Magnetically stirring for 30 minutes at normal temperature, heating to 90 ℃, and stirring and dissolving at the speed of 80 revolutions per minute;
s2, cooling, adding 9.2mL of methanol, continuously stirring to slowly form sol, finally forming gel, and sealing in the preparation process and after the gel is formed;
s3, weighing 18.7 g of aniline, and adding 30mL of 1mol/L H 2 SO 4 After stirring and dissolving, adding the gel prepared in the step S2, and standing for 4 hours;
s4, weighing 45.6g of ammonium persulfate initiator and using 30mL of H with the concentration of 1mol/L 2 SO 4 Dissolving to form a 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 S2, sealing at 0-4 ℃, and stirring for reaction 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% as a framework, wherein 1.5mol/L methanol and 0.8mol/L sulfuric acid solution are encapsulated in the framework.
Referring to the proton exchange membrane conductivity measurement method, the electrical conductivity of the sol-gel electrolyte and the liquid electrolyte at the same sulfuric acid and methanol concentrations in example 1, example 2, and example 3 were measured, respectively, and the results are shown in table 1.
Calculating the formula:
Figure BDA0003869960970000051
wherein, sigma is the conductivity, R: measurement of resistance, S: area, L: and (4) thickness.
TABLE 1 conductivity test results
Figure BDA0003869960970000052
The results in table 1 show that the PVA-PANI skeleton sol-gel electrolyte has higher conductivity than the liquid phase electrolyte.
The sol-gel electrolyte with PVA-PANI as a framework is dehydrated by gradient ethanol, is plated with platinum in vacuum after being frozen and dried by methanol and tert-butyl alcohol, and the appearance of the electrolyte is observed by a scanning electron microscope, and the result is shown in figure 1.
As can be seen from fig. 1, the sol-gel electrolyte with the PVA-PANI as the skeleton has an obvious pore structure, the skeleton is a PVA-PANI copolymer with a cross-linked structure, and the sol-gel electrolyte has good flexibility and mechanical properties, so that the properties of the electrolyte in the DMFC can be adjusted, and the pore size and the methanol mass transfer rate can be adjusted by adjusting the content of each component in the sol-gel electrolyte with the PVA-PANI as the skeleton, thereby solving the problem of methanol leakage and improving the performance of the battery.
And (3) measuring the seepage performance of the sol-gel electrolyte taking PVA-PANI as a framework by adopting a diaphragm diffusion cell method. The diffusion cell consists of two half chambers, sol-gel electrolyte with PVA-PANI as a framework is added into one half chamber on one side, and deionized water is added into the other half chamber. The Nafion 117 membrane was sandwiched between the two half chambers and was exposed to 70% sulfuric acid and 30% H prior to use 2 O 2 Soaking for 24 hours. Once an hour was taken, the methanol concentration in the deionized water side chamber was measured by gas chromatography.
The methanol bleed-out concentration versus time for the sol-gel electrolyte of example 1 and the liquid electrolyte at the same sulfuric acid and methanol concentrations are shown in fig. 2.
As can be seen in fig. 2, the methanol breakthrough concentration is linear with time.
Slope of the line:
Figure BDA0003869960970000061
the permeability coefficient P of methanol is determined from the slope of the line:
Figure BDA0003869960970000062
in the formula: v B The volume of the deionized water side chamber is 100mL, A is the membrane area 4.09cm 2 L is the film thickness, C A Is the methanol concentration.
As can be seen from FIG. 2, the slope ratio of the methanol leakage concentration-time curve of the sol-gel electrolyte and the slope ratio of the methanol leakage concentration-time curve of the liquid-phase electrolyte in example 1 are much smaller, and the permeability coefficients thereof are 6.35X 10 -8 cm 2 S -1 And 1.41X 10 - 6 cm 2 S -1 It is shown that the methanol leakage of the sol-gel electrolyte in example 1 is reduced by more than 95% compared with the liquid electrolyte, and the sol-gel electrolyte has better methanol leakage resistance.
The description and practice of the disclosure herein will be readily apparent to those skilled in the art from consideration of the specification and understanding, and may be modified and modified without departing from the principles of the disclosure. Therefore, modifications or improvements made without departing from the spirit of the invention should also be considered as the protection scope of the invention.

Claims (3)

1. A method for preparing sol-gel electrolyte of a direct methanol fuel cell is characterized in that the sol-gel electrolyte is prepared by wrapping methanol and sulfuric acid solution by using polyvinyl alcohol-polyaniline PVA-PANI as a framework, and the preparation method comprises the following steps:
s1, weighing a certain amount of polyvinyl alcohol PVA, and adding a certain amount of H with the concentration of 1-4mol/L 2 SO 4 Magnetically stirring at normal temperature for 30 minutes, heating to 90 ℃, and stirring at the speed of 80 r/min for dissolving;
s2, adding a certain amount of methanol into the solution obtained in the step S1 after cooling, slowly stirring at the speed of 60-80 rpm, and continuing stirring after sol is formed to form gel with PVA as a framework to encapsulate 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 In the process, after the materials are stirred and dissolved,adding the gel into the gel prepared in the step S2, and standing for 4 hours;
s4, weighing ammonium persulfate as an initiator according to the molar ratio of 1 2 SO 4 Dissolving to form a 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 and the methanol and sulfuric acid solution wrapped in the framework.
2. The method of claim 1, wherein in step S5, 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%.
3. The method of claim 1, wherein in step S5, the concentration of methanol in the solution of methanol and sulfuric acid encapsulated by PVA-PANI skeleton is 0.5-4mol/L, and H is higher than H 2 SO 4 The concentration is 0.5-2mol/L.
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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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