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Thin Solid Films 516 (2008) 794 797

www.elsevier.com/locate/tsf

Metal oxide nano-particles for improved electrochromic and lithium-ion

battery technologies
A.C. Dillon , A.H. Mahan, R. Deshpande, P.A. Parilla, K.M. Jones, S-H. Lee
National Renewable Energy Laboratory, 1617 Cole Blvd., Golden, CO 80401, United States
Available online 10 July 2007

Abstract
Hot-wire chemical vapor deposition (HWCVD) has been employed as an economically scalable method for the deposition of crystalline tungsten
oxide nano-rods and nano-particles. Under optimal synthesis conditions, only crystalline WO3 nano-structures with a smallest dimension of 1050 nm
are observed with extensive transmission electron microscopy (TEM) analyses. The incorporation of these particles into porous films led to profound
advancement in state-of-the-art electrochromic (EC) technologies. HWCVD has also been employed to produce crystalline molybdenum oxide nanorods, particles and tubes at high density. TEM analyses show that the smallest dimension of these nano-structures is 530 nm. XRD and Raman
analyses reveal that the materials are highly crystalline and consist of Mo, MoO2 and MoO3 phases. It is also possible to fabricate large-area porous films
containing these MoOx nano-structures. Furthermore, these films have been tested as the negative electrode in lithium-ion batteries, and a surprisingly
high, reversible capacity has been observed.
2007 Elsevier B.V. All rights reserved.
Keywords: Hot-wire chemical vapor deposition; Metal oxide nano-particles; Electrochromic; Lithium-ion battery

1. Introduction
Various transitional metal oxides including tungsten, molybdenum, vanadium, manganese, cobalt and nickel have been
investigated extensively as hosts for proton insertion (Li+, Na+,
H+). The accompanying changes in electrical and optical
properties during ion insertion/removal processes make metal
oxide nano-structures promising candidates for a variety of
applications including catalysis, gas sensors, fuel cell membranes, electrochromic (EC) windows and lithium-ion batteries
[1,2]. The kinetics of the insertion reaction is often limited by
the solid-state diffusion of the ions. Both the chemical diffusion
coefficient and the length of the diffusion path determine the
time constant of the process. While the former depends on the
chemical and crystal structure of the metal oxide, the later is
determined by the microstructure [3]. In the case of nanoparticles, the smallest dimension represents the length of the
diffusion path. Therefore, designing a nano-particle with a small
radius while maintaining the right crystalline phase is key to a

Corresponding author.
E-mail address: anne_dillon@nrel.gov (A.C. Dillon).
0040-6090/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2007.06.177

material with fast insertion kinetics and superior overall device

performance.
Recently, hot-wire chemical vapor deposition (HWCVD) has
been employed as an economically scalable method for the
deposition of crystalline tungsten oxide nano-rods and nanoparticles. Under optimal synthesis conditions, only crystalline
nano-structures with a smallest dimension of 1050 nm are
observed with extensive transmission electron microscopy
(TEM) analyses. X-ray diffraction (XRD), Raman spectroscopy
and electron diffraction confirm that the crystalline phases of the
nano-structures may be tuned by varying the synthesis
conditions such that a single phase may be obtained [4]. The
incorporation of WO3 nano-particles consisting of a mixture of
the monoclinic (I) -phase and monoclinic (II) -phase into
porous films led to a profound advancement in electrochromic
technologies that currently rely on amorphous films [5]. The
development of durable inexpensive EC materials could make
them suitable for large-area window coatings and lead to
decreased energy consumption in air conditioning.
HWCVD has also been employed to produce crystalline
molybdenum oxide nano-rods, particles and tubes at high
density. In this case a mixture of structures including MoO3,
MoO2 and Mo metal is observed, and the controlled deposition

A.C. Dillon et al. / Thin Solid Films 516 (2008) 794797

795

of a single crystalline phase has not been achieved. However,

large-area porous films containing these MoOx nano-structures
have again been fabricated. These MoOx nano-structured films
have been tested as the negative electrode (anode) in lithium-ion
batteries, and a surprisingly high reversible capacity as well as
dramatically improved charging and discharging insertion
kinetics have been shown [6]. A description of these novel
nano-structured materials and their potential for deployment in
next generation renewable energy applications is presented
here.

result, the charged particles move under the influence of an

electric field and deposit on an electrode. Since the deposition
always occurs at the anode, the metal oxide nano-particles must
attain a negative charge. The typical EDP rate is 1 m/min.
Cyclic voltammetry in a 1 M H2SO4 electrolyte solution is
employed for EC characterization and performed at room
temperature between +1.0 and 0.1 V at various scan rates. Pt
foil is used as the counter electrode and Ag/AgCl as the reference
electrode. For coloration efficiency measurements, the same
quantity of protons is inserted for each sample using a constant
current. In-situ transmittance is measured with a laser diode at
670 nm, and is recorded as a function of time using a computercontrolled potentiostat.
Before being tested in a lithium battery cell, which contains
1 M of LiClO4 in propylene carbonate (PC) as the electrolyte,
the electrodes formed from the EDP are coated with a 20 mthick solid polymer electrolyte (PEO-LiClO4). This solid
polymer electrolyte fills in all the pores in the MoOx electrode
and acts as a lithium-ion electrolyte. Once this solid polymer
adsorbs an organic solvent (PC) from the electrolyte, it becomes
an excellent ionic conductor at room temperature (with an ionic
conductivity of 2 103 S/cm). It dramatically improves the
mechanical properties of the MoOx nano-structured films as
well as the cycling stability of the electrode.

2. Experimental details

3. Results and discussion

A schematic of the HWCVD reactor is shown in Fig. 1. As

depicted in Fig. 1 a quartz tube reactor, 5 cm in diameter and
80 cm in length, is enclosed within a Mellen clamshell furnace.
The chamber is equipped with an MKS mass flow controller and
pressure control assembly as well as a mechanical roughing pump.
A single W or Mo filament, 0.5 mm diameter, 20 cm in length, or
a pair of filaments operating in series, is resistively heated to
1400 C (as measured by an optical pyrometer) in a static gas
atmosphere consisting of Ar and O2 gases. The deposition
condition variables include the furnace temperature, the total gas
pressure and the oxygen partial pressure, O2 / (Ar + O2). After the
gas ambient is stabilized at the synthesis conditions, the filament is
turned on, and a metal oxide powder collects on the walls of the
quartz tube as the filament is slowly oxidized. The deposition
parameters were independently varied to determine their effect on
nano-crystalline size and/or crystallinity. A typical deposition lasts
1520 min and 150 mg of material is obtained. The reactor has
also been employed for the bulk deposition of carbon single- [7]
and multi-wall [8] nano-tubes. For nano-tube deposition ferrocene
is employed to supply a gas phase catalyst (Fig. 1), and methane
provides the carbon source.
A unique electrophoresis deposition process (EDP) is used to
deposit thin films of the metal oxide nano-particles on SnO2:F
coated glass substrates (EC applications) or stainless steel (battery
applications). In the EDP, a nano-crystalline particle suspension is
made by dispersing 1020 mg of material in 50 ml methanol. A
magnetic stirrer is used during deposition to prevent settling. The
working and counter electrodes are separated by 10 mm, and the
voltage difference is 300 V. The EDP is based on the principle that
oxide powders suspended in a liquid attain a surface charge. As a

Fig. 2 displays a TEM image of crystalline WO3 nano-rods

and nano-speroids generated by HWCVD for synthesis
conditions where only monoclinic (I) -phase crystallites
were obtained (300 C, 150 Torr, 4% O2). Additionally, for
these synthesis conditions predominantly nano-rods were
observed with extensive TEM analyses [4]. However, for EC
applications the process was found to be optimized at 50 Torr,
16% oxygen at 300 C. In this case a mixture of various nano-

Fig. 1. HWCVD reactor for deposition of nano-structured materials.

Fig. 2. TEM image of HWCVD crystalline WO3 nano-rods and nano-speroids

generated at 300 C, 150 Torr, 4% O2.

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A.C. Dillon et al. / Thin Solid Films 516 (2008) 794797

Fig. 3. Cyclic voltammograms of a WO3 nano-particle film after a single cycle as

well as 1000 and 3000 cycles.

particle shapes consisting of either the monoclinic (I) -phase

and monoclinic (II) -phase were obtained. These nanostructures were then converted to high surface area porous
films with a thickness of 1 employing the EDP. Scanning
electron microscopy revealed that the size of the nano-particles
was not altered. Additionally, the density of the nano-particle
film was found to be 2.5 g/cm3, as estimated from mass and
thickness data. Since the theoretical bulk density of monoclinic
WO3 is 7.2 g/cm3, the pore volume of the nano-particle films
was calculated to be 0.26 cm3/g, which is comparable to those
of mesoporous metal oxides.
The electrochemical properties of the aforementioned films
were tested and compared to conventional state-of-the-art amorphous WO3 films (prepared by a vacuum deposition processes).
The electrophoresis deposited WO3 nano-particle films exhibit
vastly superior electrochemical cycling stability in an acidic
electrolyte, greater charge density, and comparable coloration
efficiency. The cycling stability of the WO3 nano-particle films
was examined in 1 M H2SO4 and is shown in Fig. 3. As evident
from the cyclic voltammograms of Fig. 3, the current response
increases slightly during 3000 cycles without significant change

Fig. 4. High-resolution TEM image of HWCVD-generated crystalline MoOx

nano-particles (75 Torr, 4% oxygen and 300 C).

Fig. 5. Chargedischarge curves for the electrode made of the nano-particles

(synthesized at 75 Torr, 4% oxygen 300 C) cycled between 3 to 0.005 Vat a C/5
rate.

in shape, indicating excellent cycling stability of nano-particle

films even in acidic solution. Under identical conditions a
conventional amorphous film significantly degraded after only
500 cycles. Also the total cathodic charge for the WO3 nanoparticles was 32 mC/cm2 mg, compared to only 9 mC/cm2 mg
for amorphous films translating to greater EC efficiency. The
exceedingly enhanced stability and charge capacity is attributed to
this first time employment of crystalline nano-particles in EC
films [5]. Furthermore, since HWCVD is an economical scalable
technique, these nano-structures may be suitable for large-area
applications.
Hot-wire chemical vapor deposition has also been employed
for the deposition of crystalline MoOx nano-particles. Optimized
nano-structured powders for Li-ion negative electrode battery
applications were obtained at 75 Torr, 4% oxygen, with the
reactor temperature at 300 C. Fig. 4 displays a high-resolution
transmission electron microscopy image of several MoO3 nanoparticles overlaid on each other where the lattice fringes are
clearly visible. In the bulk samples the particles are predominantly spherical with diameters ranging between 1025 nm,
and multiple crystalline phases are observed. However, no nonnano-particle species are detected with extensive TEM analyses.
Porous films of the MoOx nano-particles, 4 in thickness, were
again fabricated with EDP for subsequent testing as Li-ion
anodes.
The anode material most often employed in commercial
lithium-ion battery applications is graphite, and the reversible
capacity is 350 mAh/g. Fig. 5 displays the chargedischarge
curves for the electrode made of the MoOx nano-particles
synthesized at 75 Torr cycled between 3 to 0.005 V at a C/5 rate
(corresponding to 5 h of charge or discharge time). During the
first discharge cycle, the potential dropped rapidly exhibiting
two small plateaus at around 1.5 V, and then continuously
decreased down to 0.005 V. On the following cycles, the charge
discharge curves exhibit behavior that is typical to amorphous
material (without the plateau indicating phase transformation).
After the initial amorphization that was confirmed with XRD,

A.C. Dillon et al. / Thin Solid Films 516 (2008) 794797

the nano-structured MoOx electrode exhibited a reversible

capacity of 620 mAh/gm. This capacity almost doubles that of
the state-of-the-art technology. Furthermore this polymer coated
MoOx electrode showed insignificant capacity degradation for
50 cycles, (retaining 93% of its initial capacity). Additionally,
the MoOx anodes exhibit a high rate capability due to the
reduced solid-state lithium-ion diffusion length [6]. The
development of both improved cathode and anode materials
may make lithium-ion battery technologies suitable for next
generation hybrid electric vehicles.

797

nano-structures such that improved anodes may be made. The

fabrication of cathodes based on metal oxide nano-particles will
also be explored.
Acknowledgements
This work was funded by the U.S. Department of Energy
Director's Discretionary Research and Development Funding
under subcontract DE-AC36-99GO10337 to NREL.
References

4. Conclusions
Nano-structured metal oxide materials are promising for a
variety of renewable energy applications. HWCVD has been
demonstrated for the economically scalable production of
crystalline tungsten and molybdenum oxide nano-particles.
The crystalline WO3 nano-particles have been employed in
electrochromic films. Profound improvements over the conventional technology suggest that these films may be employed
in large-area EC applications. Moreover, MoOx nano-particles
have been employed in the anode of Li-ion batteries, and the
promising results indicate these materials may be further
developed for potential applications in hybrid electric vehicles.
Future work will include obtaining a better mechanistic
understanding of the lithium insertion process into the MoOx

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