Energy applications with carbon nanotubes

(1)

Energy applications with carbon nanotubes

Krisztian Kordas

Microelectronics and Materials Physics Laboratories

Department of Electrical Engineering

P.O. Box 4500, FIN-90014 University of Oulu

[email protected]

(2)

Research projects acknowledged



PrintoCent proof-of-concepts and demonstrators for commercialization, PRINDEMO_POC

(2012-2014, Tekes)



Smart and sustainable food packaging utilizing flexible printed intelligence and materials

technologies, SusFoFlex (2012-2015, EU-FP7)



High-power impulse plasma process operation for the creation of advanced metallic parts,

Hyppocamp (2013-2016, EU-FP7)



Implementation of highly efficient TiO

₂

based photocatalytic nanomaterials, Imphona (2011-2014, Tekes)



Autonomous R2R systems, AutoSys (roll-to-roll printed solar cells, 2011-2014, Tekes)



Thermal management with carbon nanotube architectures, Thema-CNT (2010-2012, EU-FP7)



Nanotechnology Platform for Electronics and Photonics, Napep (2010-2013, EU-FP7)



Optimal production of bioethanol from macroalgae via photo-chemo-enzymatic processing, OPTIFU

(2013-2015, AF)



Novel catalyst materials based on robust CNT membranes (2009-2012, AF)



Invisible electric tagging with nanomaterials, Intag (2008-2010, Tekes)



Hydrogen for fuel cells by bioethanol reforming 1-2, Reform H2 1-2 (2007-2009, Tekes)



Uusiutuvien raaka-aineiden katalyyttinen muuntaminen, Urakamu 1-2, 2007-2012, Tekes)



New, innovative sustainable transportation fuels for mobile applications, Susfuflex (2007-2010, AF)



Nanomaterials in wireless tags based on printed electronics, Printag (2005-2008, Tekes)



Integrated self-adjusting nano-electronic sensors, Sanes (2006-2009, EU-FP6)



Synthesis and implementation of highly-ordered CNT assemblies (2004-2009, AF)

(3)

General properties of CNTs

Material

Young’s modulus

(GPa)

Thermal conductivity

(W/m∙K)

Electrical resistivity

(µΩ∙cm)

Mass density

(g/cm

3

₎

Nanotubes

< 1200

< 6000

> 100

2.2 (GR)

Steel

< 220

< 65

> 10

~7.8

Epoxy

< 20

< 1.0

insulating

1.0-1.6

E. Gracia, G. Sala, F. Pino, N. Halonen, J. Luomahaara, J. Mäklin, G. Tóth, K. Kordás, H. Jantunen, M. Terrones, P. Helistö, H. Seppä, P. M. Ajayan, R. Vajtai: Electrical transport and field effect transistors using inkjet printed SWCNTs films having different functional side groups. ACS Nano 4 (2010) 3318.

N. Halonen, A. Sápi, L. Nagy, R. Puskás, A.-R. Leino, J. Mäklin, J. Kukkola, G. Tóth, M.-C. Wu, H.-C. Liao, W.-F. Su, A. Shchukarev, J.-P. Mikkola, Á. Kukovecz, Z. Kónya, K. Kordás, physica status solidi (b) 248 (2011) 2500.

(4)

Energy applications of CNTs in general

Application

Method

CNT functionality/property

Generation

Photocatalysis

Rectifying contact for photogenerated charge

separation

Solar cell

Porous large specific surface area electrical

contact

Transformation

Catalysis

Porous large specific surface area catalyst

_support

Fuel cell

Porous large specific surface area electrical

contact and catalyst support

Storage

Battery

Porous large specific surface area electrical

_{contact and support}

Capacitor

Porous inert large specific surface area

electrical contact

Fuel storage

Porous lightweight inert medium with large

_{specific surface area}

Transportation

Wiring/contact

Inert light weight flexible conductor of high

electrical and thermal conductivity

(5)

Soft electrodes for rotating and stationary contacts

•

G. Toth, J. Mäklin, N. Halonen, J. Palosaari, J. Juuti, H. Jantunen, K. Kordas, W. G. Sawyer, R. Vajtai, P. M. Ajayan, Carbon Nanotube Based Electrical Brush Contacts, Adv. Mater., 21 (2009) 2054.

Q factor of 13.2, vibrational damping

loss factor of 0.076, determined by

tan δ = Q

-1

_{= Δf/f}

r

(low to moderate

loss material)

(6)

Rotating CNT electrical contacts

•

G. Toth, J. Mäklin, N. Halonen, J. Palosaari, J. Juuti, H. Jantunen, K. Kordas, W. G. Sawyer, R. Vajtai, P. M. Ajayan, Carbon Nanotube Based Electrical Brush Contacts, Adv. Mater., 21 (2009) 2054.

(7)

Non-woven SWCNT films and pulled fibers

Acid treatment in 37 wt.% HCl for 2 days and flushing in d.i. water. Adding 2-propanol makes the films float to the top of the solvent.

 Well graphitized nanotubes

 Diameters at the range of 1~1.5 nm

Fe(C5H5)2:S8 (20:1) sublimed into the furnace at ~360 K.

Reaction at ~1270 K in Ar (1500 sccm) and CH4 (1-3

sccm). Product collected from the wall of reactor.

Synthesis by floating catalyst (iron) CVD method

Clamped film

@633 nm

L. Song, G. Toth, R. Vajtai, M. Endo, P.M. Ajayan, Carbon, 50 (2012) 5521.

L. Song, G. Tóth, J. Wei, Z. Liu, W. Gao, L. Ci, R. Vajtai, M. Endo, P.M. Ajayan, Nanotechnology 23 (2012) 015703.

(8)

Fusing currents and failure in SWCNT fibers

Ø (µm)

R (Ω)

I

_fuse

(A)

C

u

w

ire

80

1.77

127

3.62 SW

C

N

T

fiber

32 ~23

0.045

43 ~20

0.059

125 ~14

0.126

132 ~9

0.185

L. Song, G. Toth, R. Vajtai, M. Endo, P.M. Ajayan, Carbon, 50 (2012) 5521.

L. Song, G. Tóth, J. Wei, Z. Liu, W. Gao, L. Ci, R. Vajtai, M. Endo, P.M. Ajayan, Nanotechnology 23 (2012) 015703.

(9)

Halogenation of bucky papers: improved conductivity

Geza Toth, Li Song, Tommi Manninen, Melinda Mohl, Anne-Riikka Leino, Robert Vajtai, Pulickel M. Ajayan, Andrei Shchukarev, Jyri-Pekka Mikkola, Krisztian Kordas, Macroscopic carbon nanotube fibers, SIWAN 2012, Szeged, 24-27 October 2012.

1 2

3 4

If 𝑅

_𝐴

= 𝑅

_𝐵

= 𝑅, then 𝑅

_𝑆

= 𝜋𝑅 𝑙𝑛2

Van der Pauw method

𝑅

_𝐴

= 𝑉

₄₃

𝐼

₁₂

; 𝑅

_𝐵

= 𝑉

₁₄

𝐼

₂₃

𝑒

−𝜋𝑅

_𝐴

𝑅

_𝑆

_{+ 𝑒}

−𝜋𝑅

_𝐵

𝑅

_𝑆

_{= 1}

(10)

•

I_D/I_G ~0.52

ID/IG ~0.34

MWCNTs grown on (a) Inconel and (b) quartz. The scale bars in insets denote 100 nm. (c) Raman

spectra of corresponding samples.

Niina Halonen,Jani Mäklin, Anne-Riikka Leino, Jarmo Kukkola,

Antti Uusimäki, Geza Toth Leela Mohana Reddy, Robert Vajtai, Pulickel M. Ajayan and Krisztian Kordas, Chem. Phys. Lett. 583 (2013) 87.

(11)

Supercapacitor electrodes with aligned CNT forests

Niina Halonen,Jani Mäklin, Anne-Riikka Leino, Jarmo Kukkola, Antti Uusimäki, Geza Toth Leela Mohana Reddy, Robert Vajtai, Pulickel M. Ajayan and Krisztian Kordas, Chem. Phys. Lett. 583 (2013) 87.

Patterned electrodes

29.2 ± 6.1 F/g

9.1 ± 0.7 mF/cm

2

4.2 Wh/kg

133 kW/kg

Bulk electrodes

9.8 ± 3.3 F/g

5.7 ± 0.8 mF/cm

2

1.4 Wh/kg

33 kW/kg

(12)

Enhanced battery electrodes with CNT- LiFePO

₄

composites

Charge/discharge

curves

of

LiFePO

₄

electrodes. (a) Only

LiFePO

₄

(b) LiFePO

₄

and 5.4

wt.% MWCNTs, (c) LiFePO

₄

and

MWCNTs dispersed with the help

of polyoxyethylene-oleyl ether.

Ulla Lassi, Tao Hu, Elina Pohjalainen, Tanja Kallio, Krisztian Kordas, Heli Jantunen, Effect of a Surfactant Assisted Synthesis on the Electrochemical Performance of a LiFePO4-CNT Composite Electrode, International Journal of Materials Science, 2013, accepted for publication.

(a)

(b)

(c)

(b)

(c)

(13)

Solar cell counter electrodes with CNT- Pt composites

Aitola, K; Halme, J; Halonen, N (; Kaskela, A; Toivola, M; Nasibulin, AG; Kordas, K; Toth, G; Kauppinen, EI; Lund, PD, Comparison of dye solar cell counter electrodes based on different carbon nanostructures, This Solid Films 519 (2011) 8125.

(b)

CE type

R

CE

(Ωcm

2

₎

R

_{CE, ave}

(Ωcm

2

₎

C

_CE

(μFcm

− 2

₎

C

_{CE, ave}

(μFcm

− 2

₎

R

_S

(Ωcm

2

₎

R

_{S, ave}

(Ωcm

2

₎

MWCNT (pristine) on Inconel

52–57

54 270–420

340 6.5–9.0

7.8 MWCNT + Pt on Inconel

6.5–11

7.5 61–740

250 5.4–7.0

6.0 MWCNT + Pt on quartz

7.4–17

12 210–380

300 42–46

44

(14)

Chemical

functionalization

+

Dispersion / dissolution

Fuel cell with aligned CNT-Nafion

®

_{-Pt composite electrode}

Verification of working principle

Performance is to be improved by:

• Higher temperature operation (RT)  50

o

_C

• CNT/Pt  CNT/Nafion/Pt or CNT/IL/Pt composites

• Higher catalyst load (10%)  ~50%

• Better flow control

H₂ flow (15% in Ar buffer) ~35 mL/min, 1.5 bar O₂ flow (21% in N2 buffer) excess, 1.45 bar Inlet gas temperature 58 °C

300 µL 5%-Nafion® solution in MWCNT electrode

X Data

0

20

40

60

80 100 120

C

el

l po

tential

(mV)

0

200

400

600

800 1000

Current (mA) vs. Cell potential (mV)

Current (mA)

0

20

40

60

80 100 120

Po

we

r o

n

lo

a

d

(m

W)

0

10

20

Current (mA) vs. Power (mW)

(15)

N. Halonen, A. Rautio, A.-R. Leino, T. Kyllönen, G. Tóth, J. Lappalainen, K. Kordás, M. Huuhtanen, R. L. Keiski, A. Sápi, M. Szabó, Á. Kukovecz, Z. Kónya, I. Kiricsi, R. Vajtai, P. M. Ajayan. ACS Nano 4 (2010) 2003.

(16)

N. Halonen, A. Rautio, A.-R. Leino, T. Kyllönen, G. Tóth, J. Lappalainen, K. Kordás, M. Huuhtanen, R. L. Keiski, A. Sápi, M. Szabó, Á. Kukovecz, Z. Kónya, I. Kiricsi, R. Vajtai, P. M. Ajayan. ACS Nano, 4 (2010) 2003.

Hydrogenation of unsaturated hydrocarbons

a) Schematic view of the gas flow trough

catalyst scaffold. (b) Turnover rates of

propene hydrogenation to propane from 27

to 160 °C. (c) Corresponding Arrhenius plot

shows the three different catalytic reaction

regimes typical for porous solid catalysts. (d)

Aging test of catalyst shows no deactivation

after a 2 h time on stream. (e) Catalyst size

determined from TEM analysis.

(17)

Ethanol reforming on catalytic beds with CNTs

A. Sapi, R. Remias, Z. Konya, A. Kukovecz, K. Kordas and I. Kiricsi, React. Kin. Catal. Lett. 96 (2009) 379. P.K. Seelam, M. Huuhtanen, A. Sápi, M. Szabó, K. Kordás, E. Turpeinen, G. Tóth and R.L. Keiski, Int. J. Hydrogen Energy, 35 (2010) 12588.

(18)