CN102315459A

CN102315459A - Preparation method of porous fuel cell anode material NiCu/C

Info

Publication number: CN102315459A
Application number: CN201110260959A
Authority: CN
Inventors: 由宏新; 徐俊炜
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2011-09-05
Filing date: 2011-09-05
Publication date: 2012-01-11
Anticipated expiration: 2031-09-05
Also published as: CN102315459B

Abstract

Belonging to the technical field of metal material preparation, the invention relates to a preparation method of a porous fuel cell anode material NiCu/C. The method is characterized by: adopting activated carbon with a high specific surface as a hard template to impregnate a precursor solution of a metal nitrate or a metallorganic compound; in an anaerobic environment and by means of a calcination technology, carrying out heating at a proper heating rate, first decomposing the metal salt and organic compound, then subjecting the obtained metal oxide and the carbon of the hard template to a reduction reaction so as to form single metals, and finally after melting at a metal melting temperature and copying the 3D structure of activated carbon, leaving the single metals to cool to a room temperature naturally, thus obtaining a nanometer grade nickel-copper alloy material of high specific surface. And the material has an expression of MM'/C, wherein, M and M' are Ni/Cu metallic elements, and the component ratio can be distributed according to requirements. With the method of invention, a nanometer grade nickel-copper alloy material of high specific surface can be obtained through a simple and convenient operation process.

Description

The preparation method of a kind of porous fuel cell anode material NiCu/C

Technical field

The invention belongs to technical field of metal material preparation, relate to alloy and prepare process, particularly relate to the method for the loose structure characteristic of making the height ratio table.

Background technology

Advantages such as SOFC is high because of its energy conversion efficiency, and is environmentally friendly more and more cause people's attention, and there is the difficult point of carbon distribution in the research of anode material always in the SOFC.With Pt is that anode material can well solve this difficult point, but Pt costs an arm and a leg, and is difficult to be widely used.Along with deepening continuously of research; At document Preparation of Cu-Ni/YSZ solid oxide fuel cell a nodes using microwave irradiation.Shamiul Islam; Among Josephine M.Hill.Journal of Power Sources 196 (2011) 5091-5094; Researchers find that monel not only has outstanding catalytic performance, and material also has very outstanding performance to the anti-carbon aspect.It need have the characteristic of loose structure as battery anode material, and conventional preparation process adopts preparations such as sol-gel process, coprecipitation, but preparation condition and process are all very complicated.In the patent 201010100423.2; Having provided a kind of is that template prepares process through the hydrosol with carbon; Prepared a kind of PtRuNi/C ternary alloy nano catalyst, but wherein need prepare operations such as the hydrosol, acid base titration, vacuum filtration, vacuumize, experiment condition and process are complicated.

Summary of the invention

The purpose of this invention is to provide a kind of height ratio table active carbon that uses and be template; Through dipping-oven dry-approach such as calcining; The method of the monel material of simple preparation loose structure; Found a kind of Pt utmost point substitution material of moderate cost, the substitute and the monel that have solved high price Pt electrode prepare test operation in the process, the reaction condition complicated problems.

Technical scheme of the present invention and preparation method are following:

With the active carbon with high specific surface area is hard template, and the dipping precursor solution removes by filter solution, heats under the anaerobic inert atmosphere, putting into stove after the impregnated active carbon drying, and cooling promptly gets high-ratio surface porous fuel cell anode material NiCu/C.

Said precursor solution is nickel ion and the pro rata mixed solution of copper ion.

Nickel ion described in the literary composition is provided by the organic compound of nickel nitrate or nickel, preferred nickel nitrate.

Copper ion described in the literary composition is provided by the organic compound of copper nitrate or copper, preferred copper nitrate.

Need dry 1-2 hour of 110-120 as the active carbon with high specific surface area of hard template, flood precursor solution again after removing moisture and the gas of absorption, carry out subsequent treatment.

In the process of preparation precursor solution; At first according to the ratio of nickel ion and copper ion; The quality that is scaled nickel nitrate, copper nitrate takes by weighing chemicals; Again that quality is big medicine is configured to saturated solution with deionized water, and the medicine that quality is little joins in the above-mentioned saturated solution, dissolves, stirs.The ratio that the active carbon that drying is good is joined the 1g-1.5g active carbon with 5ml solution adds, and stirs 1-2 hour.

In the process that active carbon behind the dipping is calcined in heating furnace; At first can be decomposed to form cupric oxide and nickel oxide because the existence of carbon dust is arranged, under the condition of 500-600, constant temperature 1-2 hour; Cupric oxide and nickel oxide can with active carbon generation reduction reaction, produce the elemental metals copper and mickel.On the basis that the metal simple-substance copper and mickel forms, continued to be heated to 1500-1600 constant temperature 1-2 hour, the simple substance copper and mickel forms alloy in porous activated carbon, and the loose structure of meeting replication activity charcoal.

The NiCu/C material that is mixed with active carbon of provider's method preparation of the present invention can directly prepare the anode-supported fuel cell as anode material, and the active carbon in the material can directly be calcined in the battery calcination process.If need remove active carbon in advance for special circumstances, be metal simple-substance through hydrogen reducing again after can under aerobic environment, calcining, be used further to prepare the anode-supported fuel cell.

Effect of the present invention and benefit are the nickel porous Cu alloy materials that has obtained Nano grade through operating process simply and easily, can substitute the reaction of Pt electrode catalyst anode of solid oxide fuel cell.Complicated operation in the manufacturing process, the harsh problem of experiment condition have been solved.

Embodiment

Be described in detail embodiment of the present invention below in conjunction with technical scheme.

The preparation instance of NiCu/C alloy:

7.212g nickel nitrate and 5.992g copper nitrate are dissolved in the 30ml deionized water, add 6g active carbon dipping, stir half an hour, 100 times oven dry.Under oxygen-free environment; Making copper nitrate decompose in one hour at 170 times constant temperature with temperature controller respectively with 5/min speed reaches after 310 times constant temperature made that nickel nitrate decomposed in one hour; In 500 constant temperature one hour and carbon reaction reduction; Form alloy in 1500 fusings again, natural cooling is reduced to room temperature and is obtained required monel material.

Concrete temperature-rise period such as following table:

Temperature (℃)	Time (min)
		25-170	49
170-170	60
		170-310	28
310-310	60
		310-500	38
500-500	60
		500-1500	200
1500-1500	120
		1500	-121 (program stops order)

Claims

1. the preparation method of a porous fuel cell anode material NiCu/C, employing be that height ratio table active carbon is a hard template, the dipping precursor solution; Under oxygen-free environment, adopt calcine technology, earlier slaine and organic compound to be decomposed, the metal oxide and the carbon reaction reduction that decomposition are obtained are fused under the metal melting temperature at last again, and the 3D structure of replication activity charcoal; Its expression formula is MM '/C; Wherein M and M ' are the Ni/Cu metallic element, and component ratio can distribute on request, it is characterized in that M or M ' are Ni or Cu element; Hard template is the active carbon of height ratio table; Precursor solution is metal nitrate or metallo-organic compound, metal nitrate and metal-organic decomposition-reduction, the high-temperature calcination moulding under oxygen-free environment.

2. the preparation method of a kind of porous fuel cell anode material NiCu/C according to claim 1 is characterized in that the preparation process is:

With the active carbon with high specific surface area is hard template, and the dipping precursor solution removes by filter solution, heats under the anaerobic inert atmosphere, putting into stove after the impregnated active carbon drying, and cooling promptly gets high-ratio surface porous fuel cell anode material NiCu/C;

Said precursor solution is nickel ion and the pro rata mixed solution of copper ion;

Said nickel ion is provided by the organic compound of nickel nitrate or nickel, preferred nickel nitrate;

Said copper ion is provided by the organic compound of copper nitrate or copper, preferred copper nitrate;

As the active carbon with high specific surface area of hard template need 100 ℃-120 ℃ dry 1-2 hour, flood precursor solution again after removing moisture and the gas of absorption, carry out subsequent treatment;

In the process of preparation precursor solution; At first according to the ratio of nickel ion and copper ion; The quality that is scaled nickel nitrate, copper nitrate takes by weighing chemicals; Again that quality is big medicine is configured to saturated solution with deionized water, and the medicine that quality is little joins in the above-mentioned saturated solution, dissolves, stirs; The ratio that the active carbon that drying is good is joined the 1g-1.5g active carbon with 5ml solution adds, and stirs 1-2 hour; In the process that active carbon behind the dipping is calcined in heating furnace; At first can be decomposed to form cupric oxide and nickel oxide because the existence of carbon dust is arranged, under 500 ℃-600 ℃ condition, constant temperature 1-2 hour; Cupric oxide and nickel oxide can with active carbon generation reduction reaction, produce the elemental metals copper and mickel; On the basis that the metal simple-substance copper and mickel forms, continue to be heated to 1500 ℃-1600 ℃ constant temperature 1-2 hour, the simple substance copper and mickel forms alloy in porous activated carbon, and loose structure that can the replication activity charcoal.