Method and apparatus of preparing catalyst for fuel cell

Patent metadata

Field	Value
Publication number	US-11433368-B2
Application number	US-201916679718-A
Country	US
Kind code	B2
Filing date	Nov 11, 2019
Priority date	Dec 7, 2018
Publication date	Sep 6, 2022
Grant date	Sep 6, 2022

Abstract

A method for producing a catalyst for a fuel cell comprising: a) injecting carbon particles into a fluidized bed reactor; b) evacuating the fluidized bed reactor to form a base pressure; c) introducing a catalytic metal precursor together with a carrier gas into the fluidized bed reactor to contact the catalytic metal precursor with the carbon particles; d d) purging a purge gas into the fluidized bed reactor; e) introducing a reaction gas into the fluidized bed reactor to attach the catalytic metal precursor to the carbon particles; and f) purging a purge gas into the fluidized bed reactor, wherein, the catalytic metal is attached to the carbon particles in a form of nano-sized spot.

First claim

The invention claimed is:

1. A method for producing a catalyst for a fuel cell comprising:
a) injecting carbon particles into a fluidized bed reactor;
b) evacuating the fluidized bed reactor to form a base pressure;
c) introducing a catalytic platinum precursor together with a carrier gas into the fluidized bed reactor to contact the catalytic platinum precursor with the carbon particles;
d) purging a purge gas into the fluidized bed reactor;
e) introducing a reaction gas into the fluidized bed reactor to attach the catalytic platinum precursor to the carbon particles; and
f) purging a purge gas into the fluidized bed reactor,
wherein, a catalytic platinum having a nano-sized diameter is attached to the carbon particles,
the catalyst includes a carbon particle and the catalytic platinum,
a diameter of the catalytic platinum is 1 to 5 nm,
the step c) is performed for 90 to 150 seconds,
the step d) is performed for 60 to 120 seconds,
the step e) is performed for 60 to 120 seconds,
the step (f) is performed for 60 to 120 seconds,
an internal pressure of the fluidized bed reactor of steps c) to f) is 1 to 5 Torr,
the purge gas inflow rate is 50 to 200 standard cubic centimeter per minute (sccm), and
a flow rate of the reaction gas is 10 to 200 sccm.

2. The method of claim 1 ,
further comprising repeating the steps c) to f) plural times to increase the diameter of the catalytic platinum adhered to the carbon particles.

3. The method of claim 1 ,
wherein, the method further comprises a step of applying vibration to the fluidized bed reactor at 10 to 500 Hz to remove an adhesion material in a mesh located at an outlet of the fluidized bed reactor in the steps c) to f).

4. The method of claim 1 ,
wherein, in the step of evacuating the fluidized bed reactor to form a base pressure, the pressure is 0.1 to 0.5 Torr.

5. The method of claim 1 ,
wherein an inner temperature of the fluidized bed reactor in steps c) to f) is 200 to 400° C.

6. The method of claim 1 ,
wherein the catalytic platinum precursor further comprises a metal selected from the group consisting of, Co, Ru, Pd, Cu, Ni, Ag, Ir, Mo, Fe, W, Au, Rh, and combinations thereof.

7. The method of claim 6 ,
wherein the precursor including Pt comprises one selected from the group consisting of trimethyl(methacyclopentadienyl)platinum(MeCpPtMe 3 ), Platinum(II) acetylacetonate(Pt(acac) 2 ), [(1,2,5,6.η).1,5.hexadiene] dimethylpatinum(II)(HDMP), dimethyl(N,N-dimethyl-3-butene-1-amine-N)platinum(DDAP), and combinations thereof,
wherein, the precursor including Co comprises one selected from the group consisting of Bis(N,N′-di-i-propylacetamidinato)cobalt(II)(Co(iPrNCMeNiPr) 2 ), Bis(cyclopentadienyl)cobalt(II)(CoCp 2 ), Cyclopentadienylcobalt dicarbonyl(CoCp(CO) 2 ), Cobalt carbonyl (Dicobalt octacarbonyl) (Co 2 (CO) 8 ), and combinations thereof,
wherein, the precursor including Ru comprises one selected from the group consisting of Bis(cyclopentadienyl)ruthenium(Ru(Cp) 2 ), Bis(ethylcyclopentadienyl)ruthenium(II)(Ru(EtCp) 2 ), methylcyclopentadienyl ethylcyclopentadienyl ruthenium ((EtCp)Ru(MeCp)), (Me 3 NEtCp)RuCp, Cyclopentadienyl ethyl (dicarbonyl) Ruthenium(Ru(Cp)(CO) 2 Et), N,N-Dimethyl-1-ruthenocenylethylamine (RuCp(CpCh(Me)(NMe 2 ))), Tris(2,2,6,6-tetramethyl-3,5-heptanedionato) ruthenium(III)(Ru(thd) 3 ), Bis(N,N-di-t-butylacetamidinato)ruthenium(II) dicarbonyl(Ru(tBuAMD) 2 (CO) 2 ), Rudic, Carish, and combinations thereof,
wherein, the precursor including Pd comprises one selected from the group consisting of Palladium(II) hexafluoroacetylacetonate(Pd(hfac) 2 ), Palladium tetramethylheptanedionate(Pd(thd) 2 ), palladium-ketoiminato(Pd(keim 2 ) 2 ), and combinations thereof,
wherein, the precursor including Cu comprises one selected from the group consisting of Copper(I) chloride(CuCl), Copper(II) hexafluoroacetylacetonate hydrate(Cu(hfac) 2 ), Copper(II) acetylacetonate(Cu(acac) 2 ), Copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate)(Cu(thd) 2 ), Bis(dimethylamino-2-propoxy)copper(II)(Cu(dmap) 2 ), Bis(N,N′-di-i-propylacetamidinato)copper(II)([Cu(iPrNCMeNiPr)] 2 ), Bis(N,N′-di-sec-butylacetamidinato)dicopper(I)([Cu(sBuNCMeNsBu)] 2 ), and combinations thereof,
wherein, the precursor including Ni comprises one selected from the group consisting of Bis(N,N′-di-i-propylacetamidinato)nickel(II)(Ni(iPrNCMeNiPr) 2 ), Nickel(II) acetylacetonate(Ni(acac) 2 ), Nickel Heptafluoroisopropyl(Ni(hfip) 2 ), and combinations thereof,
wherein, the precursor including Ag comprises one selected from the group consisting of (2,2-dimethylpropionato)silver(I)triethylphosphine(Ag(O 2 CtBu)(PEt 3 )), (1,5-Cyclooctadiene)(hexafluoroacetylacetonato)silver(I)(Ag(hfac)(cod)), and combinations thereof,
wherein, the precursor including Ir comprises one selected from the group consisting of Iridium(III) acetylacetonate(Ir(acac) 3 ), iridium(ethylcyclopentadienyl)(1,5-cyclooctadiene)(Ir(EtCp)(cod)), 1-Ethylcyclopentadienyl-1,3-cyclohexadieneiridium(I)(Ir(MeCp)(chd)), and combinations thereof,
wherein, the precursor including Mo comprises MoCl 5 ,
wherein, the precursor including Fe comprises Bis(N,N′-di-sec-butylacetamidinato)iron(I)(Fe(iBuNCMeNtBu) 2 ), and
wherein, the precursor including W comprises WF 6 .

8. The method of claim 1 ,
wherein, the carbon particles comprise one selected from the group consisting of carbon black, graphene, CNTs, and combinations thereof.

9. The method of claim 1 ,
wherein, the reaction gas comprises one selected from the group consisting of O 2 , O 3 , Air, H 2 , NH 3 , H 2 plasma, NH 3 plasma, and O 2 plasma.

10. The method of claim 1 ,
wherein, the purge gas comprises argon gas, helium gas or nitrogen gas.

11. The method of claim 1 ,
before a) the step of injecting carbon particles into the fluidized bed reactor,
the method further comprises a step of filling glass beads into an interior part of a mesh located at an outlet of the fluidized bed reactor and an outer part of a mesh located at the inlet of the fluidized bed reactor.

12. The method of claim 1 ,
wherein, the purge gas comprises argon gas,
wherein, the reaction gas comprises an oxygen gas,
wherein, the carbon particles comprise carbon black, and
wherein, the platinum catalytic precursor comprises trimethyl(methacyclopentadienyl)platinum (MeCpPtMe 3 ).

13. The method of claim 1 , wherein the purge gas inflow rate is 60 to 120 sccm.

14. The method of claim 1 , wherein the catalytic platinum precursor comprises trimethyl(methacyclopentadienyl)platinum(MeCpPtMe 3 ).

Assignees

• Hyundai Motor Co Ltd
• Kia Motors Corp
• Nat Univ Pusan Ind Univ Coop Found

Inventors

• Hong Woong Pyo
• Kwon Se Hun
• Lee Woo Jae

Classifications

• B01J23/74

  Iron group metals · CPC title

• B01J2208/00017

  Controlling the temperature · CPC title

• B01J8/40 Primary

  with fluidised bed subjected to vibrations or pulsations · CPC title

• H01M4/921

  Alloys or mixtures with metallic elements · CPC title

• C23C16/45529

  specially adapted for making a layer stack of alternating different compositions or gradient compositions · CPC title