CN1489232A

CN1489232A - Method for preparing carbon-carried platinum/rare earth oxide composite electro catalyst for fuel cell

Info

Publication number: CN1489232A
Application number: CNA021384142A
Authority: CN
Inventors: 刘晶华; 孙延先; 佘沛亮; 陈怀林
Original assignee: LONGYUAN SHUANGDENG POWER SUPPLY CO Ltd JIANGSU
Current assignee: LONGYUAN SHUANGDENG POWER SUPPLY CO Ltd JIANGSU
Priority date: 2002-10-10
Filing date: 2002-10-10
Publication date: 2004-04-14
Anticipated expiration: 2022-10-10
Also published as: CN100356619C

Abstract

Based on traditional technique, aqueous solution containing rare earth ion and precipitant aqueous solution are added. Then, heat treatment is carried out. Platinum and rare earth in electrocatalyst made from the invention plays concerted catalysis effect in electrocatalysis oxidizing reaction of methanol, improving dynamics of electrocatalysis and oxidizing reaction. Comparing with traditional Pt/C catalyzer, exchange current density of anode reaction of methanol fuel cell is increased 48-70%. The method possesses advantages of easy implementation, without need of special equipment, good stability and repeatability.

Description

The preparation method of fuel cell carbon-carried platinum/rare earth oxide composite electrocatalyst

Technical field

The present invention relates to the preparation method that a kind of carbon carries platinum/rare earth oxide composite electrocatalyst, belong to the fuel cell technology field.

Background technology

Advantages such as fuel cell is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) that directly chemical energy of fuel is converted into electric energy, has the energy conversion efficiency height, and environmental pollution is little are considered to following the most promising clean energy resource.Proton Exchange Membrane Fuel Cells in the fuel cell especially is subjected to common attention in recent years, because this kind fuel cell have other kind types of fuel cells incomparable advantage such as cold operation, all solid state etc., at present each major company all competitively infusion of financial resources research and develop.Yet at present Proton Exchange Membrane Fuel Cells mainly uses hydrogen to act as a fuel, and has storage, carry critical defects such as inconvenience and danger, infrastructure have high input.Therefore people have proposed the notion of direct methanol fuel cell, this be since its to have a fuel cost low, be easy to store advantage such as carry.

In the development of direct methanol fuel cell, the preparation of eelctro-catalyst is the key that influences battery performance, traditional eelctro-catalyst preparation method adopts chloroplatinic acid aqueous solution is joined in the active carbon suspension-turbid liquid, add the method that reducing agent is precipitated out platinum again and make the carbon platinum-carrying electrocatalyst, this conventional method exists a deficiency, the electrocatalysis oxidation reaction dynamics speed of methyl alcohol is slower on the eelctro-catalyst that promptly makes, and eelctro-catalyst is to the intermediate product that contains carbonyl of methyl alcohol anode electrocatalysis oxidation reaction, comparatively responsive as micromolecule such as CO, lose the part catalytic activity thereby easily poisoned, cause the output power density of galvanic anode lower thus by it.Anode reaction exchange current density with methyl alcohol on the eelctro-catalyst of conventional method preparation is 8.6 * 10 ^-7A/cm ², the initial oxidation current potential is 0.24V in the cyclic voltammetry experiment, peak current density is 24mA/cm ²

Summary of the invention

The objective of the invention is to overcome the active low deficiency of conventional P t/C catalyst, provide a kind of carbon to carry the preparation method of platinum/rare earth oxide composite electrocatalyst, this method is a raw material with platinum and rare earth oxide, difunctional synergy takes place in the composite electrocatalyst middle rare earth and the platinum that make, and is final from having improved the dynamics speed of methyl alcohol anode electrocatalysis oxidation reaction in essence.

Preparation method's the concrete implementation step that carbon of the present invention carries platinum/rare earth oxide composite electrocatalyst is as follows:

(1) under 60 ℃-95 ℃, active carbon is evenly spread in three distilled water and be mixed with suspension-turbid liquid with supersonic oscillations or high-strength mechanical agitation method;

Drip platinum acid chloride solution when (2) stirring, continue then to stir 2 hours;

(3) slow dropping or spray add the excessive reducing agent aqueous solution under inert gas shielding, continue then to stir 24 hours;

(4) adding concentration is the rare earth ion aqueous solution of 0.5-4mol/L, and wherein rare earth ion is any in the ion of europium, holmium, dysprosium, gadolinium, and the scale of rare earth element and the mol ratio of pure chloroplatinic acid are 1: 1-1: 3, continue then to stir 0.5-2 hour;

(5) adding concentration is the precipitation reagent aqueous solution of 1-20wt%, and wherein precipitation reagent is any in sodium carbonate, potash, oxalic acid, the sodium oxalate, and the weight ratio of the scale of precipitation reagent scale and rare earth element is 2: 1-4: 1, continue then to stir 2-24 hour;

(6) filter, after washing, the drying with the catalyst that makes under 950 ℃ of-1200 ℃ of inert gas shieldings heat treatment 1-5 hour.

Become electrode with the Preparation of Catalyst that makes, its exchange current density is 1.27 * 10 ^-6A/cm ²-1.46 * 10 ^-6A/cm ², improved 48-70% than conventional method; The initial oxidation current potential is 130-180mV in the cyclic voltammetry experiment, than the negative 60-110mV that moved of conventional method; Peak current density is 34.3-42mA/cm ², increased 43-75% than conventional method.

Embodiment

Embodiment 1:

Under 60 ℃, active carbon is evenly spread in three distilled water and be mixed with suspension-turbid liquid with supersonic oscillations or high-strength mechanical agitation method;

Dropping platinum acid chloride solution when stirring continues to stir 2 hours then, slowly drips or spray then to add the excessive reducing agent aqueous solution under inert gas shielding, continues to stir 24 hours again;

Adding concentration is the europium ion aqueous solution of 0.5mol/L, and wherein the mol ratio of the scale of europium and pure chloroplatinic acid is 1: 1, continues then to stir 0.5 hour;

Adding concentration is the aqueous sodium carbonate of 1wt%, and wherein the weight ratio of the scale of sodium carbonate scale and europium is 2: 1, continues then to stir 2 hours;

Filter, after washing, the drying with the heat treatment 1 hour under 950 ℃ of inert gas shieldings of the catalyst that makes.

Become electrode with the Preparation of Catalyst that makes, its exchange current density to the anodic oxidation of methanol reaction is 1.39 * 10 ^-6A/cm ², improving 62% than Pt/C eelctro-catalyst, the initial oxidation current potential is 150mV in the cyclic voltammetry experiment, moves 90mV than Pt/C eelctro-catalyst is negative, peak current density is 38.4mA/cm ², increase by 60% than Pt/C eelctro-catalyst.

Embodiment 2:

Under 95 ℃, active carbon is evenly spread in three distilled water and be mixed with suspension-turbid liquid with supersonic oscillations or high-strength mechanical agitation method;

Adding concentration is the gadolinium ion aqueous solution of 4mol/L, and wherein the mol ratio of the scale of gadolinium and pure chloroplatinic acid is 1: 3, continues then to stir 2 hours;

Adding concentration is the sodium oxalate aqueous solution of 20wt%, and wherein the weight ratio of the scale of sodium oxalate scale and gadolinium is 4: 1, continues then to stir 24 hours;

Filter, after washing, the drying with the heat treatment 5 hours under 1200 ℃ of inert gas shieldings of the catalyst that makes.

Become electrode with the Preparation of Catalyst that makes, its exchange current density to the anodic oxidation of methanol reaction is 1.46 * 10 ^-6A/cm ², improving 70% than Pt/C eelctro-catalyst, the initial oxidation current potential is 130mV in the cyclic voltammetry experiment, moves 110mV than Pt/C eelctro-catalyst is negative, peak current density is 42mA/cm ², increase by 75% than Pt/C eelctro-catalyst.

Embodiment 3:

Under 70 ℃, active carbon is evenly spread in three distilled water and be mixed with suspension-turbid liquid with supersonic oscillations or high-strength mechanical agitation method;

Adding concentration is the holmium ion aqueous solution of 1mol/L, and wherein the mol ratio of the scale of holmium and pure chloroplatinic acid is 1: 1.5, continues then to stir 1 hour;

Adding concentration is the wet chemical of 5wt%, and wherein the weight ratio of the scale of potash scale and holmium is 3: 1, continues then to stir 8 hours;

Filter, after washing, the drying with the heat treatment 2 hours under 1000 ℃ of inert gas shieldings of the catalyst that makes.

Become electrode with the Preparation of Catalyst that makes, its exchange current density to the anodic oxidation of methanol reaction is 1.27 * 10 ^-6A/cm ², improving 48% than Pt/C eelctro-catalyst, the initial oxidation current potential is 180mV in the cyclic voltammetry experiment, moves 60mV than Pt/C eelctro-catalyst is negative, peak current density is 34.3mA/cm ², increase by 43% than Pt/C eelctro-catalyst.

Embodiment 4

Under 90 ℃, active carbon is evenly spread in three distilled water and be mixed with suspension-turbid liquid with supersonic oscillations or high-strength mechanical agitation method;

Adding concentration is the dysprosium ion aqueous solution of 3mol/L, and wherein the mol ratio of the scale of dysprosium and pure chloroplatinic acid is 1: 2, continues then to stir 1.5 hours;

Adding concentration is the oxalic acid aqueous solution of 15wt%, and the weight ratio of the scale of its mesoxalic acid scale and dysprosium is 3.5: 1, continues then to stir 20 hours;

Filter, after washing, the drying with the heat treatment 4 hours under 1100 ℃ of inert gas shieldings of the catalyst that makes.

Become electrode with the Preparation of Catalyst that makes, its exchange current density to the anodic oxidation of methanol reaction is 1.41 * 10 ^-6A/cm ², improving 64% than Pt/C eelctro-catalyst, the initial oxidation current potential is 140mV in the cyclic voltammetry experiment, moves 100mV than Pt/C eelctro-catalyst is negative, peak current density is 37.4mA/cm ², increase by 56% than Pt/C eelctro-catalyst.

Claims

1, the preparation method of a kind of fuel cell carbon-carried platinum/rare earth oxide composite electrocatalyst comprises the following steps: that (1) evenly spreads to active carbon in three distilled water to be mixed with suspension-turbid liquid; Add platinum acid chloride solution when (2) stirring; (3) slowly add the reducing agent aqueous solution; (4) filtration, washing, drying; It is characterized in that further comprising the steps of:

After adding platinum acid chloride solution and adding the reducing agent aqueous solution, add the aqueous solution that contains rare earth ion, then slowly add the precipitation reagent aqueous solution, heat-treat after step is finished more than all.

2, by the preparation method of the described fuel cell carbon-carried platinum of claim 1/rare earth oxide composite electrocatalyst, it is characterized in that except that filtration, washing, drying and heat treatment step the temperature of suspension-turbid liquid remains at 60 ℃-95 ℃ in other step.

3,, it is characterized in that the rare earth ion that adds is any in the ion of europium, holmium, dysprosium, gadolinium by the preparation method of the described fuel cell carbon-carried platinum of claim 1/rare earth oxide composite electrocatalyst.

4, press the preparation method of the described fuel cell carbon-carried platinum of claim 1/rare earth oxide composite electrocatalyst, it is characterized in that the scale of the rare earth element that adds and the mol ratio of pure chloroplatinic acid are 1: (1-3), the concentration of the aqueous solution middle rare earth ion that contains rare earth ion that adds is 0.5-4mol/L, adds the back and stirs 0.5-2 hour.

5, press the preparation method of the described fuel cell carbon-carried platinum of claim 1/rare earth oxide composite electrocatalyst, it is characterized in that the precipitation reagent that adds is any in sodium carbonate, potash, oxalic acid, the sodium oxalate, the weight ratio of the scale of precipitation reagent scale and rare earth element is (2-4): 1, the concentration of precipitation reagent in its aqueous solution is 1-20wt%, adds the back and stirs 2-24 hour.

6, by the preparation method of the described fuel cell carbon-carried platinum of claim 1/rare earth oxide composite electrocatalyst, it is characterized in that described heat treatment is to carry out under 950 ℃ of-1200 ℃ of inert gas shieldings, the time is 1-5 hour.