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Tolga Kaya
Central Michigan University
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temperature inside the box is kept at 150C for Zn and 225C for Cu. Heating time for the Cu
and Zn layer were 30 minutes and 20 minutes, respectively. After sintering, the sample is cut into
two pieces: one half remains untreated, while the other half is soaked with an ionic liquid;
1-Butyl-3-methylimidazolium (Sigma-Aldrich), with 1 drop (0.1g)/mm2 [2].
RESULTS AND DISCUSSION
The SEM picture of Zn and Cu nanoparticles are taken under 30,000 magnification. It can
clearly be seen from Fig. 1a and b that aggregation was a problem. Therefore, an additional
1 hour of sonication was performed in order to separate them completely before dispersing them
into the base fluid. The particle shape and size are the main parameters to determine the melting
point of the nanoparticles. After examining Fig. 1c and d, the process temperature was optimized
so that the particles would melt but not get oxidized.
Figure 1. (a) and (b) the aggregation of Zn and Cu nanoparticles. (c) and (d) the smaller scale for
individual groups of nanoparticles.
Fig. 2 shows detailed SEM images of the coated samples. Fig. 2a shows a cross-sectional
view of the film. Surface cracks during the process can degrade the conductivity (Fig. 2c). As
can be seen from Fig. 2d-f, coating process with the Mayer rod was successful.
The dielectric response was investigated with a dielectric spectrometer, consisting of an
Agilent 4294A impedance analyzer and a Sigma Systems M10 temperature chamber. The
frequency was swept from 40 Hz to 5 MHz at temperatures from 30 C to 70 C. Battery
samples made of paper without ionic liquid show a strong relaxation at approximately 200 Hz
and 70 C, which is not found in plain commercial paper. This indicates that the solvent for
nanoparticle suspension may have seeped into the paper during the coating processes, and did
not evaporate completely later. The permittivity is found to be 19 for a sample without ionic
liquid (w/out) and 210 for the sample with the ionic liquid (w/).
Figure 2. SEM photographs of the coated samples. (a) Cross-sectional image of a paper sample
without ionic liquid. (b) and (c) Surface of copper coated by hand. (d) Surface of zinc coated by
hand. (e) Surface of copper coated with Mayer rod. (f) Surface of zinc coated with a Mayer rod.
Figure 3. Dielectric spectrum of the paper battery samples with and without ionic liquid. Sample
without the ionic liquid, real part (a); Imaginary part (b). Sample with the ionic liquid, real
part(c); Imaginary part (d).
Figure 4. (a) The first charging cycle of samples with and without ionic liquid. (b) The first
discharge cycle of these samples.
Our slurry making process was very successful so that the uniform suspension and
dispersion were maintained for more than two weeks. The optimization included the variation of
the particle density of zinc and copper in the slurry. We tested the viscosity of the slurry with
various concentration ratios and found that 1:2 (nanoparticle: base fluid) worked the best. The
base fluid for the zinc nanoparticles is 1-methyl-2-pyrrlidone (NMP), and diethylene glycol
monobutyle for the copper nanoparticles.
The rheology tests were performed by using a rheometer (TA instruments AR 2000) with a
parallel plate that has the diameter of 40 mm. The shear rate is swept from 0.01 s-1 to 100 s-1 at
25 C, 70 C and 80 C. Coating was done at room temperature. However, higher temperature
measurements will become very important as the coating is performed with a printer, which
would eventually require higher temperature applications.
The results from Fig. 5 show that the Cu and Zn suspension exhibited non-Newtonian
behavior, and the viscosity increased with higher volume concentration at the same temperature.
0.2000
viscosity (Pa.s)
1.000E-3
1.000E-5
1.000E-4
1.000E-3
0.01000
0.1000
shear stress (Pa)
1.000
10.00
100.0
Figure 5. The rheology measurement of viscosity vs shear stress for zinc and copper
nanosuspension.
As the temperature increases the viscosity of copper and zinc nanosuspension decreases
exponentially, however the copper suspension shows more dramatically at shear stress higher
than 0.01 Pa. That means, in those heat sensitive experiments, these nanoparticles need to be
treated very carefully because the viscosities decrease dramatically as temperature increase.
The coated result may not be successful due to collapse of particle connectivity which implies a
decrease in the viscosity [11, 12].
CONCLUSIONS
We propose the use of Copper (Cu) and Zinc (Zn) nanoparticles as the electrodes for
thin-film microbatteries in the applications of micro-scale sensors. Commercial paper was used
as the separator to demonstrate the battery performance. Paper that acts as the separator is
slurry-casted with nanoparticles (30-40 nm in size) on both sides. The electrodes were developed
to achieve high conductivities (lower than 1 ( cm)-1) with smooth surface, good adhesion, and
flexibility. The metal nanoparticles will be formulated to slurry solutions for Mayer rod coating
for the battery fabrication. For fabrication purposes, the slurries viscosity is approximately in the
range of 0.04-0.2 Pa.s at the operating temperature. During the fabrication process including
coating and sintering, reductive environment is required to minimize the oxidation.
Batteries were tested with and without an ionic liquid for comparison. Characterization
results included rheology measurements, dielectric spectroscopy, charging and discharging
curves, and SEM (Scanning Electron microscopy) of the particles.
Our research suggest that conductive paper can be scalable and could make
high-performance energy storage and conversion devices at low cost and would bring new
opportunities for advanced applications.
ACKNOWLEDGEMENTS
The authors would like to thank Kevin Petsch for his help with the picoammeter parameter
settings, Avtar Batth for the dielectric measurements, Yi Xu for setting up the sintering
equipment, and Nalinda Almeida for his help with viscosity measurements. The discussions with
Dr. Joyce from Western Michigan University, Center for the Advancement of Printed Electronics,
and suggestions from staff of the Lurie Nanofabrication Facility, University of Michigan, Ann
Arbor, were also appreciated.
REFERENCES
1. F.Isabel, B.Bruno, C.Nuno, B.Pedro, F.Elvira, and M. Rodrigo J. Display Technology, 6, 8
(2010)
2. C. C. Ho, J. W. Evans, and P. K. Wright, J. Micromech. Microeng. 20, 104009. (2010).
3. C. C. Ho, K. Murata, D. A. Steingart, J. W. Evans, and P. K. Wright, J. Micromech.
Microeng. 19, 094013 (2009).
4. S. Gamerith, A. Klug, H.Scheiber, U. Scherf, E. Moderegger, and J. W. Emil, Advanced
Functional Materials. 17, 3111-3118 (2007).
5. L. B. Hu, J. W. Choi, Y. Yang, S. Jeong, F. L. Mantia, L. F. Cui, and Y. Cui, PNAS
0908858106. (2009).
6. E. K. Yu, L. H. Piao, and S. H. Kim, Bull. Korean Chem. Soc. 32. 11 (2011)
7. H. S. Kim, S. R. Dhage, D. E. Shim, and H. T. Hahn, Applied Physics A. 97, 791-798 (2009).
8. W. S. Han, J. M. Hong, H. S. Kim, and Y. W. Song, Nanotechnology. 22, 395705. (2011).
9. J. S. Kang, H. S. Kim, J. Ryu, H. T. Hahn, S. Jang, and J. W. Joung, J Mater. Sci: Mater
Electron. 21, 1213-1220. (2010).
10. D. J. Lee, S. H. Park, S. Jang, H. S. Kim, J. H. Oh, and Y. W. Song, J. Micromech. Microeng.
21, 125023 (2011).
11. D.P Kulkarni, D.K.Das, G.A Chukwu. Journal of nanoscience and nanotechnology. 6,
1150-1154. (2006).
12. J. Bicerano, J.F. Douglas, D.A. Brune. Journal of Macromolecular Science Review. 39:
561-642. (1999).