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Thin-film Micro-Batteries Based on Metal


Nanoparticles
ARTICLE in MRS ONLINE PROCEEDING LIBRARY JANUARY 2012
DOI: 10.1557/opl.2012.1490

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Tolga Kaya
Central Michigan University
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Thin-film Micro-Batteries Based on Metal Nanoparticles


Shuang Peng1, Wenjun Du2,3, Leela Rakesh3,4, Axel Mellinger1,3, and Tolga Kaya3,5
1

Department of Physics, 2Department of Chemistry, 3Science of Advanced Materials Program,


4
Department of Mathematics, 5School of Engineering and Technology
Central Michigan University, Mount Pleasant, MI, 48859, U.S.A.
INTRODUCTION
Thin film batteries are a universal high-technology hot topic, and material researchers in
different fields are making efforts to develop new materials and better fabrication methods for
the thin film batteries. Using nanomaterials, they can me made lighter and more flexible for
applications such as sensors and electronic devices. Moreover, the flammability is lower by using
nanoparticles for the electrodes. With copper (Cu) and zinc (Zn) thin film electrodes, coated on a
commercial paper acting as separator and mechanical support, a rechargeable battery can be
formed. Paper itself has found itself numerous applications mainly thanks to its high porosity and
robust chemical and mechanical stability [1].
Battery fabrication based on nanoparticle and ink printing technology has become quite
popular and the results are promising including carbon nanotubes to the metal nanoparticles, for
example silver and zinc based structures. Dispensing an ionic liquid using a special printer with
the electrodes, researchers from UC Berkeley have achieved good results [2, 3]. Moreover,
dispersions based on silver-copper nanoparticles were also developed which can be used as the
electrodes for organic field-effect transistors [4]. Researchers from Stanford have fabricated a
highly conductive paper coated of single-walled carbon nanotube and silver nanowire film,
which shows an excellent performance as energy storage devices [5].
EXPERIMENTAL PROCEDURES
Various techniques for slurry preparing were investigated. The following is the optimized
procedure: (a) Sonication of 0.2 g zinc nanoparticles in a water bath (VWR B3500A-MT) for 1
hour, (b) mixing with 0.6g 1-methyl-2-pyrrlidone (NMP), (c) shaking for 20 seconds
(Vortex-Genie 2, Model G560) at a speed of 9 cycles/s, or stirring it for 20 s (Fisher Scientific
Model 50 Sonic Dismembrator) at 45 Hz, (d) further sonication of the slurry for 2 hours (VWR
B3500A-MT). The copper slurry was made by 1:2 (wt) of copper nanoparticles and diethylene
glycol monobutyl ether (>92% Sigma-Aldrich). The same procedures were applied for the Zn
slurry. Cu and Zn slurries were coated on commercial printer paper using a Mayer rod.
The sintering temperature depends on the particle size and the melting point of the
nanomaterials. Here we used a particle size ranging from 30-50 nm. We used a metal box
mounted on a hot plate with nitrogen gas inlets for passing through formic acid in order to
prevent the oxidation of particles at high temperatures [6]. The flow rate is 20 CFH, and the

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).

Charging and discharging characterization of the battery devices were performed by


applying a constant voltage of 2.5 V and monitoring the current levels via a computer controlled
picoammeter (Keithley Model 6485). The discharging tests were conducted without an external
load since the sample itself has a high internal resistivity. As Fig. 4 depicts, sample with the ionic
liquid produced higher current levels (approximately 100 times more). Both charging and
discharging tests lasted for 1 hour.

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)

copper and zinc suspension viscosity vs shear stress

Zn 1 SSF 25, Flow Step


Zn 1 SSF 70, Flow Step
Zn 1 SSF 80, Flow Step
Cu 1 SSF 25, Flow Step
Cu 1 SSF 70, Flow Step
Cu 1 SSF 80 , Flow Step

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.
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