CN103151534A

CN103151534A - Direct methanol fuel cell (DMFC) nano PdNi (lead nickel)/mesoporous TiO2 (titanium dioxide) membrane anode and preparation method thereof

Info

Publication number: CN103151534A
Application number: CN2013100877273A
Authority: CN
Inventors: 鞠剑峰; 吴东辉; 石玉军; 章琴; 苏广均; 华平; 李建华
Original assignee: Nantong University
Current assignee: Nantong University
Priority date: 2013-03-19
Filing date: 2013-03-19
Publication date: 2013-06-12
Anticipated expiration: 2033-03-19
Also published as: CN103151534B

Abstract

The invention discloses a direct methanol fuel cell (DMFC) nano PdNi (lead nickel)/mesoporous TiO2 (titanium dioxide) membrane anode and a preparation method thereof. The product consists of a titanium plate and a nano PdNi/mesoporous TiO2 membrane catalyst. The DMFC nano PdNi/mesoporous TiO2 membrane anode is compounded by the nano PdNi/mesoporous TiO2 membrane catalyst and the titanium plate, wherein the nano PdNi/mesoporous TiO2 membrane catalyst consists of PdNi nano alloy and high specific surface mesoporous TiO2 membrane. PdNi alloy can be used for improving the conductivity of TiO2, the synergistic effect of PdNi to TiO2 can be used for improving the catalytic oxidation performance of TiO2 to methanol, and at the same time, CO (carbon monoxide) and the like intermediate products generated by methanol oxidation are adsorbed and transmitted to the surface of the composite membrane catalyst and are directly deeply oxidized into the end product CO2 (carbon dioxide), so that the CO poisoning capability resistance of the catalyst is improved; due to the price of PdNi far lower than that of precious metals such as Pt (platinum) and Ru (ruthenium), and the dosage of PdNi in the membrane catalyst is little, and the compounding of PdNi and the titanium plate is used for the anode of a DMFC, so that the manufacturing cost of the DMFC can be greatly reduced, and the performance of the DMFC is improved.

Description

The mesoporous TiO of direct methanol fuel cell nanometer PdNi/ 2Film anode and preparation method

Technical field

The present invention relates to the mesoporous TiO of a kind of direct methanol fuel cell nanometer PdNi/ ₂Film anode and preparation method.

Background technology

Direct methanol fuel cell (Direct Methanol Fuel Cell, DMFC) have that less energy consumption, energy density are high, the methyl alcohol source is abundant, low price, system are simple, the convenient and low noise advantages of operation, be considered to future automobile power and the most promising chemical power source of other vehicles, cause people's extensive concern.One of material of DMFC most critical is electrode catalyst, and it directly affects performance, stability, useful life and the manufacturing cost of battery.Precious metals pt (less than 80 ℃) under cryogenic conditions has excellent catalytic performance, the electrode catalyst of DMFC is all take Pt as main component at present, wherein the PtRu catalyst has stronger anti-CO poisoning performance and the catalytic activity of Geng Gao than pure Pt, the catalyst that is considered to present DMFC the best, but the defectives such as, Ru Yi Rong expensive due to it, the utilance in DMFC does not also reach business-like requirement.People have carried out large quantity research and have prepared multiplex catalyst to improve its catalytic activity, improve the resisting CO poison ability.Prepared PtRuTiO if any report _X/ C and Au/TiO ₂The PtRu catalyst, TiO ₂The compound consumption that can reduce precious metals pt in catalyst improves catalytic performance and resisting CO poison ability, has application prospect.The mesoporous TiO of nanometer PdNi/ ₂Film catalyst is a kind of non-platinum catalyst, and methyl alcohol is had good catalytic performance and resisting CO poison performance, and the film anode that is compounded to form with the titanium plate can be used as the direct methanol fuel cell anode, is not reported.

Summary of the invention

The object of the present invention is to provide a kind of direct methanol fuel cell anode that can be used as, reduce direct methanol fuel cell catalyst cost, improve the mesoporous TiO of direct methanol fuel cell nanometer PdNi/ of its catalytic activity and resisting CO poison ability ₂Film anode and preparation method.

Technical solution of the present invention is:

The mesoporous TiO of a kind of direct methanol fuel cell nanometer PdNi/ ₂The film anode is characterized in that: the mesoporous TiO of described direct methanol fuel cell nanometer PdNi/ ₂The film anode is by titanium plate and the mesoporous TiO of nanometer PdNi/ ₂Film catalyst is composited; Titanium plate thickness 0.3 mm, purity 99.5 %, film catalyst intermediary hole TiO ₂Content be 95 ~ 99 %, the content sum of nanometer PdNi is 5 ~ 1 %, above-mentioned content is mass percent, the mol ratio 1:1 of PdNi.

The mesoporous TiO of described direct methanol fuel cell nanometer PdNi/ ₂The preparation method of film anode is characterized in that: comprise the following steps:

1) pre-treatment of titanium plate: the titanium plate is polished with abrasive paper for metallograph, and ultrasonic oil removing is 15 minutes in acetone, then successively through methyl alcohol or ethanol clean, the HF of 1 mol/L processes 10 minutes, redistilled water ultrasonic cleaning 3 times, oven dry;

2) press the mesoporous TiO of PdNi/ ₂W in film catalyst _PdNi=1 % ~ 5%, mol ratio n _Pd: n _NiFor 1:1 calculates, with the PdCl of amount of calculation ₂And NiCl ₂With absolute ethyl alcohol and deionized water dissolving, form solution, wherein, the volume of absolute ethyl alcohol is identical with step 3), and the deionized water quality is half of deionized water quality in step 3);

3) TiO ₂The preparation of colloidal sol: the butyl titanate of amount of calculation is dissolved in absolute ethyl alcohol, adds the surfactant Pluronic P-123 (EO of the amount of adding under stirring ₂₀PO ₇₀EO ₂₀, Aldrich, molecular weight 5800), drip the mixture of absolute ethyl alcohol, glacial acetic acid and deionized water after dissolving, drip step 2 after 1 hour) solution that forms, continuing to stir, hydrolysis forms colloidal sol; During preparation colloidal sol, the consumption mol ratio of butyl titanate, surfactant Pluronic P-123, absolute ethyl alcohol, glacial acetic acid, deionized water is: n _{Butyl titanate}: n _P-123: n _{Absolute ethyl alcohol}: n _{Glacial acetic acid}: n _{Deionized water}=1:0.01 ~ 0.02:20 ~ 40:1 ~ 2.5:2 ~ 6;

4) colloidal sol that step 3) is made adopts the surperficial spin-coating film of the titanium plate of spin coating instrument after processing, humidity 30%, and 3000 rev/mins of gluing speed were painted with in 30 seconds, titanium plate surface formation glued membrane; 8 ℃ of spin-coating films are after aging 5 days, with 450 ℃ of roastings of titanium plate vacuum 2 hours except the surfactant Pluronic P-123 in striping, then 500-600 ℃ of nitrogen atmosphere roasting 3 hours the mesoporous TiO of titanium plate surface recombination nanometer PdNi/ ₂The mesoporous TiO of the nanometer PdNi/ of film catalyst ₂The film anode.

The present invention is with the mesoporous TiO of PdNi Nanoalloy and high-ratio surface ₂The mesoporous TiO of nanometer PdNi/ that film forms ₂Film catalyst and titanium plate are composited.The PdNi alloy improves TiO ₂Conductivity and to TiO ₂Synergy improve TiO ₂To the catalytic oxidation performance of methyl alcohol, simultaneously, the intermediate products such as CO that methanol oxidation produces are adsorbed, transfer to the film catalyst surface, and are end product CO by direct deep oxidation ₂, can improve the resisting CO poison ability of catalyst, due to the price of PdNi far below noble metals such as Pt, Ru, and its consumption is less in film catalyst, therefore can greatly reduce the cost of catalyst, and is compound with the titanium plate, can directly be used as the direct methanol fuel cell anode, improve battery performance.

The invention will be further described below in conjunction with embodiment.

Embodiment:

Embodiment 1:

1) pre-treatment of titanium plate: the titanium plate is polished with abrasive paper for metallograph, and ultrasonic oil removing is 15 minutes in acetone, more successively through methyl alcohol or ethanol clean, the HF of 1 mol/L processes 10 minutes, redistilled water ultrasonic cleaning 3 times, oven dry.

2) press the mesoporous TiO of PdNi/ ₂W in film catalyst _PdNi=1 %, mol ratio n _Pd: n _NiFor 1:1 calculates, with the PdCl of amount of calculation ₂And NiCl ₂With a certain amount of absolute ethyl alcohol and deionized water dissolving, form solution, wherein, the volume of absolute ethyl alcohol is identical with step 3), and the deionized water quality is half of water quality in step 3);

3) TiO ₂The preparation of colloidal sol: the butyl titanate of amount of calculation is dissolved in a certain amount of absolute ethyl alcohol, adds the surfactant Pluronic P-123 (EO of the amount of adding under stirring ₂₀PO ₇₀EO ₂₀, Aldrich, molecular weight 5800), drip the mixture of absolute ethyl alcohol, glacial acetic acid and deionized water after dissolving, approximately drip step 2 after 1 hour) solution that forms, continuing to stir, hydrolysis forms colloidal sol.During preparation colloidal sol, the consumption mol ratio of butyl titanate, surfactant P-123, absolute ethyl alcohol, glacial acetic acid, deionized water is: n _{Butyl titanate}: n _P-123: n _{Absolute ethyl alcohol}: n _{Glacial acetic acid}: n _{Deionized water}=1:0.01 ~ 0.02:20 ~ 40:1 ~ 2.5:2 ~ 6.

4) colloidal sol that step 3) is made adopts the surperficial spin-coating film of the titanium plate of spin coating instrument after processing.Humidity 30%, 3000 rev/mins of gluing speed were painted with in 30 seconds, titanium plate surface formation glued membrane.8 ℃ of spin-coating films are after aging 5 days, with 450 ℃ of roastings of titanium plate vacuum 2 hours except the P-123 in striping, then 500-600 ℃ of nitrogen atmosphere roasting 3 hours the mesoporous TiO of titanium plate surface recombination nanometer PdNi/ ₂The mesoporous TiO of the nanometer PdNi/ of film catalyst ₂The film anode.

Embodiment 2:

Press last synthetic catalyst W in step (2) _PdNi=3 %, all the other are with embodiment 1.

Embodiment 3:

Press last synthetic catalyst W in step (2) _PdNi=5 %, all the other are with embodiment 1.

Claims

1. mesoporous TiO of direct methanol fuel cell nanometer PdNi/ ₂The film anode is characterized in that: the mesoporous TiO of described direct methanol fuel cell nanometer PdNi/ ₂The film anode is by titanium plate and the mesoporous TiO of nanometer PdNi/ ₂Film catalyst is composited; Titanium plate thickness 0.3 mm, purity 99.5 %, film catalyst intermediary hole TiO ₂Content be 95 ~ 99 %, the content sum of nanometer PdNi is 5 ~ 1 %, above-mentioned content is mass percent, the mol ratio 1:1 of PdNi.

2. mesoporous TiO of direct methanol fuel cell nanometer PdNi/ claimed in claim 1 ₂The preparation method of film anode is characterized in that: comprise the following steps:

3) TiO ₂The preparation of colloidal sol: the butyl titanate of amount of calculation is dissolved in absolute ethyl alcohol, the surfactant Pluronic P-123 that adds the amount of adding under stirring, drip the mixture of absolute ethyl alcohol, glacial acetic acid and deionized water after dissolving, dropping step 2 after 1 hour) solution that forms, continue to stir, hydrolysis forms colloidal sol; During preparation colloidal sol, the consumption mol ratio of butyl titanate, surfactant Pluronic P-123, absolute ethyl alcohol, glacial acetic acid, deionized water is: n _{Butyl titanate}: n _P-123: n _{Absolute ethyl alcohol}: n _{Glacial acetic acid}: n _{Deionized water}=1:0.01 ~ 0.02:20 ~ 40:1 ~ 2.5:2 ~ 6;