Nanocatalizadores bimetlicos de Co-Ni decorados con Pt

para Celdas de Combustible de Intercambio Protnico

Ernesto Flores Rojas

Advisor: Omar Solorza Feria
Co-Advisor: Juan Francisco Prez

Content
Abstract

1. Introduction
2. Experimental Procedure
3. Results and Discussion
4. Conclusions

Abstract
Bimetallic Solid Solutions (NiCo) with several compositions
used as core were synthesized
by High Energy Ball Milling
Technique
(HEBM)
and
supported on Carbon.
Bimetallic Solid Solutions
(BSS) decorated with Pt by
the Galvanic Displacement
Process (GDP) to form
electrocatalysts for PEM FC

1. INTRODUCTION
There are two types of cells:
Galvanic Cells (G<0).
ElectroChemical Cells (G>0).

Components of Cells
Electrolyte
Catalysts
Redox agents

PEM Fuel Cell

The hydrogen Proton
Exchange Membrane or
Polymer
Electrolyte
Membrane Fuel Cell (PEM
FC) converts chemical
energy
directly
into
electrical energy with the
single product of water.
Kinetic of the
sluggish ORR

Challenges on PEM FC
Durability
Cost
Performance (efficiency)

-Degradation of Membranes.
-Corrosion and Dislolution
of Carbon.
-Pollution of fuel cell
components

Use less Pt and improve its utilization

Alloy Pt with transition metals: Pt M
Non-Pt catalysts
Platinum
particle
size,
crystallite geometry, metal
dispersion on the carbon
support, conductivity, and
porosity of the catalyst layer.
6

Challenges on Catalysts for PEMFC

Electronic
Configuration

Specific Mass
Mass Activity
Electrochemical
Surface Area
Catalyst
Interaction

Size, morphology,
geometry
and
shape of particles
for selective lattice
planes and surfaces

Material-Support

Catalysts Configuration
Core-shell structures, multimetallic nanoparticles or
non-noble
metal-based
catalysts have attracted
attention due to their novel
physical
and
chemical
properties arising from their
combined effects.

HEBM
The High Energy Ball Milling (HEBM) is
a used technique for phase metastable synthesis, solid state reactions,
Mechanical Alloying or fabrication of
Solid Solutions

Goals
To synthesize electrocatalysts
To analyze and characterize electrocatalysts

Perspectives
Application of electrocatalysts in PEM FC

10

2. Experimental Procedure
Solid solutions and metallic materials were prepared by highenergy ball-milling technique using a SFM-1 (QM - 3SP2) High
Speed Shimmy Ball Mill.
Synthesis of bimetallic systems
System (% at.)

Ratio (wt.)
Ball:Material

Material Vial /
Material Ball

Time
(hours)

PCA

Co100

5:1

Al2O3 / Iron

65

Ethanol/Isopropyl

Co70 Ni30

5:1

Al2O3 /Iron

65

Ethanol/Isopropyl

Co50 Ni50

5:1

Al2O3 /Iron

65

Ethanol/Isopropyl

Co30 Ni70

5:1

Al2O3 /Iron

65

Ethanol/Isopropyl

Ni100

5:1

Al2O3 /Iron

60

Ethanol/Isopropyl

Dispersed On Carbon
Vulcan XC-72R was used to disperse and support.
Bimetallic Solid Solution powders in Isopropyl Alcohol were
sonochemically processed with a Ultrasonic Processor VC
505 (500watts).

12

Galvanic Replacement
Carbon-supported bimetallic Solid Solutions
dispersed with TBAB. Metal:Dispersant Ratio 1:1
Pt precursor reagent added as K2PtCl6.

Reflux at 160 C during 8 hours.

Pt about 20% wt. metal ratio.
REACTION

Pt2+ + 2e- Pt(s)

Co2+ + 2e- Co(s)
Ni2+ + 2e- Ni(s)

E/V

+1.2
-0.277
-0.250
13

Characterization
XRD

Physical

EDS
TEM

STEM

Characterization

Linear

Oxygen

Voltammetry

Reduction

Electrochemical
CV

Cyclic
Voltammetry

CO

Stripping
14

Electrochemical measurements
Ink was coated and dried at
65 C on a polished glassy
carbon-disk. The loadings Pt
were about 20 g/cm2.

15

3. Results and
Discussion
Physical Characterization

XRD of Co100
2 Theta
20
23.14
32.95
38.84
40.65

Co

Intensity (a. u.)

1500

60 h

1000

45 h
500

30 h

15 h

10

20

30

40

50

60

Intensity
1000
400
250
300
120

70

2 Theta (degrees)

XRD patterns for Co100 ball milled for several times and TEM micrographs.

XRD of Ni100
1500

Intensity (a. u.)

Ni

2 Theta
20.13
23.27
33.15
39.09
40.9
52.16
53.62

1000

60 h

45 h
500

30 h

15 h
0
10

20

30

40

50

60

70

2 Theta (degrees)

XRD patterns for Ni100 ball milled for several times.

Intensity
1000
420
210
200
70
140
150

Co30-Ni70

1500

60 h

1000

45 h

Co70-Ni30

1500

Intensity (a. u.)

Intensity (a. u.)

CoO

Co
Ni
CoO
60 h

1000

45 h
500

30 h

500

30 h
15 h

15 h

0
10

20

30

40

50

60

70

2 Theta (degrees)

Intensity (a. u.)

20

30

40

50

60

70

2 Theta (degrees)

Co50-Ni50

1500

10

CoO

TEM micrograph of Co70-Ni30

ball milled for 15h

60 h

1000

45 h

30 h

500

15 h

10

20

30

40

50

60

70

2 Theta (degrees)

XRD patterns for Co30-Ni70, Co50-Ni50 and Co70-Ni30 ball milled for several times.

TEM micrographs of Co30-Ni70@20Pt/C

TEM micrographs of Co30-Ni70@20Pt

STEM micrographs of Co50-Ni50@20Pt/C

STEM micrographs Co50-Ni50@20Pt/C

STEM micrographs of Co70-Ni30@20Pt/C

STEM micrographs Co70-Ni30@20Pt/C

STEM micrographs of Co70-Ni30@20Pt/C

STEM micrographs dark field (left) and bright field Co70-Ni30@20Pt/C

Electrochemical Characterization
Cyclic Voltammetry Co@20%Pt LPt = 20 g/cm2geo - Scan Rate: 50 mV/s

Current Density [mA/cm2 real]

0.1

Series1

0.0
0.0

-0.1

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

E [V RHE]

CV profiles Co100 @20Pt/C in 0.1M HClO4

1.1

1.2

1.3

CV Final

Electrochemical Results
Current Density [mA/cm2geo]

Co100@20Pt/C
Co70Ni30@20Pt/C

-1

Co50Ni50@20Pt/C
Ni100@20Pt/C

-2

-3

-4

0.0

0.2

0.4

0.6

0.8

1.0

E [VRHE]

ORR polarization curves of four several catalysts; Co100@20Pt/C, Co70Ni30 @20Pt/C,

Co50Ni50@20Pt/C and Ni100@20Pt/C after 25 CV scans at room temperature;
conditions: 0.1 M HClO4, 20 mV/s, O2 atmosphere, 1600 rpm.

Electrochemical Results
0.50

Co100@20Pt/C
Co70Ni30@20Pt/C

0.45

B0 = 1/m
Material
[mA cm-2 rpm1/2]
8.13
12.29
Co100@20Pt/C
9.17
10.89
Co70Ni30@20Pt/C
10.01
9.98
Co50Ni50@20Pt/C
8.87
11.26
Ni100@20Pt/C

Co50Ni50@20Pt/C
j-1 [mA/cm2]-1

0.40

Ni100@20Pt/C

0.35
0.30
0.25
0.20
0.15
0.020

0.025

0.030

0.035

0.040

0.045

0.050

w-1/2 [rpm-1/2]

KouteckyLevich plot and theoretical path n = 4e for Co100@20Pt/C,

Co70Ni30@20Pt/C, Co50Ni50@20Pt/C and Ni100@20Pt/C after 25 CV scans at room
temperature; conditions: 0.1 M HClO4, 20 mV/s, O2 atmosphere, 1600 rpm.

Electrochemical Results
Material

Co100@20Pt/C

Co70-Ni30@20Pt/C

Co50-Ni50@20Pt/C

Co30-Ni70@20Pt/C

Ni100@20Pt/C

Catalyst
number

Electrochemical Specific Activity Mass Activity

Surface Area
(mA/cm2pt)
(mA/mg pt)
[m2/g]
at 0.9 V
at 0.9 V

20.64

0.0099

22.35

0.0461

10

12.06

0.2192

26

06.14

0.2314

14

09.71

0.1802

18

09.73

0.2057

20

12.80

0.2689

26

11.53

0.5790

67

36.52

0.2623

96

34.97

0.2423

85

Conclusions
Solid solutions and bimetallic systems show a good
performance in specific density respect to the system with a
single metal Co100@20Pt/C.
Co100@20Pt/C has the poorest activities.
Specific Activity is higher than Mass Activity in all systems.

Ni100@20Pt/C has the highest activities.

TO BE CONTINUED