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Seminar Report 2011-2012 Nanowire batteries for next generation

electronics
ABSTRACT
The scaling of electronic devices also requires the evolution of high energy density
power sources. By using nanowires, high charge storage materials, which otherwise have
mechanical breakage problems due to large structure transformations and volume changes,
can be adopted as electrode materials. High power operation can also be possible due to the
short lithium insertion distances in the nanowires. We have studied Si and Ge nanowires and
demonstrated charge storage capacities several times higher than the graphite anodes used in
existing battery technology.LiMn2O4 nanorod cathodes were found to show much higher
power rates than commercial powders.
Detailed morphology and structure characterization have shown that these

improvements are attributed to facile strain relaxation, good electronic contact and
conduction, and short Li insertion distances in the nanowire battery electrode. We also
developed a Langmuir-Blodgett assembly technique to produce nanowire pillars as battery
electrodes, which opens up the possibility for the fabrication of on-chip battery power
sources.
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INTRODUCTION
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The scaling of electronic devices such as transistors,memories and hard-disks has
induced a revolution in the electronics industry. For portable electronics such as cell phones
OR
and laptops, it is necessary to have corresponding power sources to evolve as well. Li-ion
rechargeable batteries have been the dominating power source. To match the future scaling of
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electronics, higher energy density (and specific energy) rechargeable batteries are desirable.
The existing Liion battery technology consisting of a graphite anode (370 mAh/g) and
LiCoO2 cathode (170 mAh/g) has limited charge storage capacity and energy density,
making it necessary to explore new electrode materials. There are several high storage
capacity materials suitable for making a higher energy density anode. For example, Si and Ge7
can alloy with large amounts of lithium to give theoretical capacities of 4200 mAh/g and
1600 mAh/g, respectively. However, one common problem of high charge storage materials
is that the alloying process results in large structural transformations and volume changes. In
bulk materials, these large volume changes can cause the electrode to crack and pulverize
(Fig. 1a).
Figure 1. Schematic of morphological changes that occur in Si duringelectrochemical

cycling. A) Si films and particles tend to pulverize during cycling, resulting in poor transport
of electrons, as indicated by the arrow. B) Facile strain relaxation in the NWs allows them to
increase in diameter and length without breaking.
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Often times, this leads to material losing electronic contact to the current collector
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over time, which results in poor cycle life. Using the material in a nanowire (NW)
morphology has several advantages. First, the small NW diameter allows for better
OR
accommodation of the large volume changes without the initiation of fracture that can occur
in bulk or micron-sized materials. Second, NWs have direct 1D electronic pathways allowing

for efficient charge transport. One drawback to using nanoparticles, for example, is that they
must be assembled into a composite containing conducting carbon and binders to maintain
good electronic conduction throughout. Electronic charge carriers must move through small
interparticle contact areas in these electrodes, but in nanowire electrodes the carriers can
move efficiently down the length of each wire.
7
Finally, several nanowire synthesis methods allow for vertically oriented growth on
various types of substrates. Thus, nanowires can be grown directly on the metallic current
collector. This is a clear advantage as every NW is connected to the currentcarrying
electrode, and moreoever the need for binders or conducting additives, which add extra
weight, is eliminated. We have explored the use of nanowires of high capacity materials for
battery electrodes (1). By using Si and Ge nanowires grown using the vapor-liquid-solid
growth as an example, we showed that NWs do not break when undergoing large structural
and volume changes. Both Si and GeNWs can provide a charge storage capacity close to their
theoretical capacities, with SiNWs displaying a capacity 10 times higher than in graphite
anodes. We also demonstrated a Langmuir- Blodgett assembly technique to produce SiNW
pillars as battery electrodes, which opens up the possibility for the fabrication of on-chip
battery power sources.
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RESULTS
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Li insertion into the SiNWs was found to exhibit higher capacities than other forms
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of Si or graphite. Fig. 2a shows the first and second cycles at the C/20 rate (20 hours to
charge or discharge). The voltage profile observed was consistent with previous studies on Si

anodes, with a long flat plateau during the first charge, during which amorphous LixSi is
formed from crystalline Si. Subsequent discharge and charge cycles have different voltage
profiles, characteristic of amorphous silicon. The discharge capacity was ~3100 mAh/g with
little fading over 10 cycles and a coulombic efficiency >90% (Fig. 2b). As a comparison, our
data are shown along with those reported for thin films containing 12 nm Si nanocrystals
8
(NCs) and graphite carbon in Fig. 2b. This improved capacity and cycle life in the SiNWs
indicates the advantage of their small diameter. The SiNWs displayed a good power
performance as well. Fig. 2c shows the charge and discharge curves observed at 10 hr (C/10),
5 hr (C/5), 2 hr (C/2), and 1 hr (1C) rates. Even at the 1C rate, the capacities remained >2100
mAh/g, which is ~ 6 times of graphite. Under constant capacity charging (1043 mAh/g, >3
times of graphite), we have been able to achieve 145 cycles with 95% capacity retention,
which shows promise for commercialization(Fig. 2d).
Figure 2a. The voltage profiles for the first and second galvanostati
cycles of the SiNWs
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OR
10
Figure 2b. Capacity vs. cycle number for the SiNWs at the C/20 rate
compared to Si nanocrystals and graphite.
Figure 2d. Cycling of SiNWs using a fixed charge of 0.12 mAh (1043 mAh/g).
To understand the high capacity and good cyclability ofour SiNW electrodes, we
studied the structural morphology changes. Fig. 3a shows scanning electron microscopy
(SEM) images of SiNWs before and after lithiation.
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Fig. 3b shows the change in the diameter distribution of the NWs. The diameter of
the SiNWs expands by 50% after Li insertion. An important observation is that despite the
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large volume change,the SiNWs remain intact and have not broken into smaller particles. The
SiNWs also change their length during the volume change (Fig. 3c). To evaluate this, 25 nm
OR
Ni was evaporated onto the SiNWs before cycling to serve as an inert backbone. Afterwards,
the morphology of the SiNWs suggested that length expansion of the NW was impeded by

connection to the Ni, instead leaving the NW in a helical shape around the Ni. With both a
diameter and length increase, the SiNW volume change after Li insertion appears to be about
300%. The detailed transmission electron microscopy (TEM) studies (Fig. 3d) showed that
the SiNWs change from a single crystalline to an amorphous structure during lithiation in the
first cycle and remain amorphous thereafter.
10
Figure 3a. Scanning electron microscopy images of SiNWs before and after cycling.
Figure 3b. Size distribution of NWs before and after charge to 10mV (bin size 10 nm). The
average diameter of the NWs increased from 89 to 141 nm.
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OR
Figure 3c.Transmission electron microscope image of a pristine SiNW with a partial Ni

coating before and after Li cycling.
10
Fig. 3d. Transmission electron microscopy images of SiNW becoming amorphous during
lithiation
We have developed a CMOS compatible process to fabricate SiNW battery electrodes

for on-chip power sources. As shown in Fig. 4, the Langmuir-Blodgett method is used to
assemble SiO2 nanoparticles on a Si wafer. We have obtained monolayers of particles
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covering a 4” wafer surface. The nanoparticles, which function as an etch mask, can have
diameters controllably tuned using reactive ion etching (RIE). RIE was also used to produce
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vertical nanopillars with controllable diameters and spacings from 50nm to 1000nm. We have
exploited these NW pillars as well-defined anodes for lithium batteries.
OR
10
Figure 4. Schematic representation of the fabrication of Si

nanopillars with corresponding scanning electron microscope
images.
Finally, the general advantages of NW battery electrodes shown in this paper have
also been demonstrated in other materials. We have also demonstrated high capacity GeNW
anodes (2) and high rate LiMn2O4 nanorods cathodes (3). The LiMn2O4 nanorods were
found to display high charge storage capacities at high power operation with good
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reversibility and cyclability (Fig. 5). The nanorods performed significantly better than
commercially available powders with particle sizes around 10 μm at the higher rates.
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OR
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Figure 5. Scanning electron microscope image of LiMn2O4 nanorods. Evaluation of the
nanorods at high power rates showed better capacity retention compared to commericial
powders (particle size ~ 10 μm).
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CONCLUSIONS
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We have found that Si and Ge nanowires can perform as suitable high capacity
OR
anodes for Li-ion batteries. The good structural properties of the NWs allows for large
volume changes to occur without pulverization. We have also found that LiMn2O4 nanorods
can display better power operation than bulk commercial powders. Having shown these
systems as examples, we believe that nanowire battery electrodes have the the potential to
greatly improve the energy and power delivered to the class of next generation electronics.
10
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ADVANTAGES OF THE NANOWIRE BATTERY

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Many advantages arise with the use of the silicon nanowire battery. This battery can
OR
be used with laptops, iPods, cell phones, digital cameras and video cameras. Although the
technology has evolved tremendously, companies with traveling businessmen, the movie

industry, delivery trucks and perhaps even hospitals can benefit from this battery.
Of course, computers are essential to all businesses. A laptop is used by many
business people as they save many company documents that they may need outside of the
office. Business people who have to make a presentation or people who are frequent fliers
10
will benefit from a longer battery life. It can be risky to rely on laptops as it is very difficult
to find a wall plug when needed. In the short run, this battery can create a competitive
advantage for companies who manufacture laptops with this new battery. Also, business
people will always be able to remain in touch with their companies with cell phone that hold
a longer battery life as well. Consumers’ interest in laptops that hold a charge for twenty
hours will encourage people to replace their laptops causing sales to increase. In the long run,
this battery will probably become the standard battery of a laptop.
Another industry that can benefit from the silicon nanowire battery is the movie
industry or filming companies as the battery holds the charge of video cameras as well. While
filming a movie, people will no longer have to worry about tripping over wires or moving too
far away from the wall plug. Also, people who film parties or weddings will no longer have
to worry about being obtrusive to the guests at the party.
In the future, this battery can work in the favour of delivery trucks. If the battery is
going to work on electric cars, there is a possibility of it being beneficial to electric trucks as
well. Using the silicon nanowire battery, delivery trucks will be able to drive a must longer
distance without needing to fill up for gas or charge their truck. This can save companies a lot
of money as many companies have numerous trucks on the road simultaneously.
Further, the battery might be used for medical equipment in the future. Hospitals that
have machines running on electricity will be able to perform surgeries when there is a power
failure. With the silicon nanowire battery, machines will be able to last for hours without
having to be recharged.
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DISADVANTAGES anytime
OF THE NANOWIRE BATTERY
As with every new product, there are several disadvantages to the new silicon
OR
nanowire battery; car companies will have to design new cars, products operating on lithium-
ion batteries will become obsolete.
First, if electric cars become the way of the future, car companies will have to invest a
lot of money into product design. Although electric cars exist today, car companies will have
to design a variety of new models to incorporate the new nanowire battery. Since consumer’s
10
interest in cars that run on gas will severely decrease, it will be necessary for companies to
introduce many cars with the nanowire battery.
Second, products made with a lithium-ion battery will be considered obsolete. Once
the silicon nanowire batteries become popular, like other technologies, consumers will not
want to purchase them. This is a disadvantage for technology companies as they will have to
redesign their products incorporating the nanowire battery. This can be become expensive
and many small to medium size businesses may not be able to afford this. Technology is ever
changing and companies have to be able to keep up with the times to stay afloat.
Third, at first, most companies will want to create products using the silicon nanowire
battery to test it in the market. Since it will be a on trial basis, cell phone companies or Apple
may only make a limited number of cell phones or iPods using the new battery. If advertised
well, many consumers will want to purchase the product once it is on sale. The products with
the nanowire battery will probably sell out quickly causing many companies to have a
waiting list or back-orders. Unfortunately, this causes companies to lose out on potential
profits. Companies will have to devote a lot of resources to creating these new products and
try to not run out of stock too quickly.
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THE SILICON anytimeBATTERY
NANOWIRE
OR
10
Have you ever been in the middle of an important phone call on your cell phone and a
couple minutes into the call your phone battery just died? A new information technology will
change rechargeable batteries for our gadgets as we know it.Stanford researchers discovered
a way to create the new silicon nanowire battery which is a rechargeable battery that can hold
ten times more power than the batteries used today.
Dr. Yi Cui, Assistant Professor of Material Science and Engineering

at Stanford University invented this revolutionary development. In an interview, he explained
that silicon nanowires have been around for quite some time but they have never been applied
to batteries before. He has filed for a patent and hopes to partner up with a battery
manufacturing company to bring the new silicon nanowire battery into the market soon.
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WHAT CAN THECancel anytime

NANOWIRE BATTERY REPLACE?
OR
The silicon nanowire battery is expected to replace the lithium-ion battery. For

example, with the lithium ion battery, a fully charged laptop can last for approximately two
hours. Using the nanowire battery, a laptop’s battery life will last ten times longer; hence the
battery life will be extended to twenty hours!
The lithium-ion battery’s anode, usually made with carbon material, has a limited
10
quantity of lithium it can store. Stanford researchers discovered that if the carbon is replaced
by silicon nanowires, the battery can store
ten times more lithium allowing the battery
to have a much longer battery life.
When the battery is charged, Dr. Yi

Cui and his staff realized that as the battery
absorbs positively charged lithium
components, the silicon swells. When the
battery is in use, the lithium atoms are
released from the silicon allowing the silicon to shrink. This growing and shrinking can be
compromising to the battery performance. For this reason,nanotechnology is implemented
meaning lithium is placed in tiny nanowires allowing for the silicon to resist breakage.
A nanowire battery is a lithium-ion battery invented by a team led by Dr. Yi

Cui at Stanford University in 2007. The team's invention consists of a stainless
steel anode covered in silicon nanowires, to replace the traditional graphite anode. Silicon,
which stores ten times more lithium than graphite, allows a far greater energy density on the
anode, thus reducing the mass of the battery. The large surface area further allows for fast
charging and discharging.
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DESIGN
OR
Traditional silicon anodes were researched and dismissed due to the tendency of
silicon to crack and become unusable because it swelled with lithium during operation. The

nano-wires do not suffer from this flaw. According to Dr. Cui, the battery reached 10x
density on the first charge and plateaued to 8x density on subsequent charges. In order to
take advantage of this anode advancement, an equivalent cathode advancement is required to
achieve the increased storage density.
10
Commercialization is expected to occur in 2012 with the batteries costing the same or
less per watt hour than conventional lithium-ion batteries. The next milestone, life cycle
testing, should be completed and the team expects to achieve at least one thousand charge
cycles from nano-wire batteries. In September 2010, Dr. Yi Cui's team demonstrated that 250
charge cycles are possible before the charge capacity drops below 80 percent of its initial
storage capacity. The team expects to reach 3,000 charge cycles by 2012. Reaching this goal
would make nano-wire batteries viable for use in electric vehicles. A prototype for use in
cellular phones and other electronic devices was expected to be delivered by the first quarter
of 2011.
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POTENTIAL PROBLEM
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The very high surface area of the nanowires, which allows high charging rates, also
has a downside: heterogeneous side reactions.These will occur as the nanowires on the
OR
negative electrode are brought below around +0.8 V, where the electrolyte becomes
thermodynamically unstable and starts getting reduced .The result will be a film made from

decomposition products that coats the surfaces of the nanowires.This coating, called a "solid
electrolyte interphase (SEI)," is present in all Li-ion batteries that use conventional
electrolytes and low voltage electrodes such as graphite or silicon. Typically, the active
particles on the negative electrode side (graphite) are around 10 microns in diameter. While
10
such large sizes extract a penalty by lowering the surface area and power, that size is
necessary in order to reduce the amount of SEI formed (which is proportional to the surface
area). Even so, 5-10% of all of the Li in a Li-ion battery ends up incorporated into the SEI,
leading to an irreversible capacity loss (ICL) of that amount. (The source of the Li in a cell is
mainly the positive electrode, such as LiFePO4.) Fortunately, the SEI formation reactions are
self-limiting, and after the first cycle ICL can be very small.
On the other hand, a nanowire might have a couple of orders of magnitude more
surface area per unit volume than a 10 micron particle, which would result in a couple of
orders of magnitude more SEI formed—except that there is not enough Li in the positive
electrode to make this much SEI. The result of this loss of accessible Li would be a drastic
loss of capacity after the first cycle. Nanowire cells can nevertheless cycle hundreds of times
in half-cells. In a half cell, an electrode made from a piece of Li metal would be cycled
against the nanowires. Since in a half cell there is a nearly unlimited supply of Li, capacity
need never decline. Such half cells, however, would have no commercial value. There are
tricks that can be employed to reduce ICL—for example, by pre-forming the SEI before
assembling the cell. However, this process is not done commercially because of the high cost
of adding such a processing step.
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NANOWIRE
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A nanowire is a nanostructure, with the diameter of the order of a nanometer
(10−9 meters). Alternatively, nanowires can be defined as structures that have a thickness or
OR
diameter constrained to tens of nanometers or less and an unconstrained length. At these
scales, quantum mechanical effects are important — which coined the term "quantum wires".

Many different types of nanowires exist, including metallic (e.g., Ni, Pt, Au), semiconducting
(e.g., Si, InP,GaN, etc.), and insulating (e.g., SiO2, TiO2). Molecular nanowires are composed
of repeating molecular units either organic (e.g. DNA) or inorganic (e.g. Mo6S9-xIx). The
nanowires could be used, in the near future, to link tiny components into extremely
small circuits. Usingnanotechnology, such components could be created out of chemical
compounds.
10
Overview
Typical nanowires exhibit aspect ratios (length-to-width ratio) of 1000 or more. As

such they are often referred to as one-dimensional (1-D) materials. Nanowires have many
interesting properties that are not seen in bulk or 3-D materials. This is because electrons in
nanowires are quantum confined laterally and thus occupy energy levels that are different
from the traditional continuum of energy levels or bands found in bulk materials.
Peculiar features of this quantum confinement exhibited by certain nanowires

manifest themselves in discrete values of the electrical conductance. Such discrete values
arise from a quantum mechanical restraint on the number of electrons that can travel through
the wire at the nanometer scale. These discrete values are often referred to as the quantum of
conductance and are integer values of
They are inverse of the well-known resistance unit h/e2, which is roughly equal to
25812.8 ohms, and referred to as the von Klitzing constant RK (after Klaus von Klitzing, the
discoverer of exact quantization). Since 1990, a fixed conventional value RK-90 is accepted.
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Examples of nanowires include inorganic molecular nanowires (Mo6S9-xIx,
Li2Mo6Se6), which can have a diameter of 0.9 nm and be hundreds of micrometers long.
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Other important examples are based on semiconductors such as InP, Si, GaN, etc., dielectrics
(e.g. SiO2,TiO2), or metals (e.g. Ni, Pt).
OR
There are many applications where nanowires may become important in electronic,

opto-electronic and nanoelectromechanical devices, as additives in advanced composites, for
metallic interconnects in nanoscale quantum devices, as field-emitters and as leads for
biomolecular nanosensors.
10
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SYNTHESIS OF NANOWIRES
OR
10
There are two basic approaches of synthesizing nanowires: top-down and bottom-up
approach. In a top-down approach a large piece of material is cut down to small pieces
through different means such as lithography and electrophoresis. Whereas in a bottom-up
approach the nanowire is synthesized by the combination of constituent ad-atoms. Most of
the synthesis techniques are based on bottom-up approach.Nanowire structures are grown
through several common laboratory techniques including suspension, deposition
(electrochemical or otherwise), and VLS growth.
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USES OF NANOWIRES
OR
Nanowires still belong to the experimental world of laboratories. However, they may
complement or replace carbon nanotubes in some applications. Some early experiments have
shown how they can be used to build the next generation of computing devices.To create
active electronic elements, the first key step was to chemically dope a semiconductor
nanowire. This has already been done to individual nanowires to create p-type and n-type
semiconductors.
10
The next step was to find a way to create a p-n junction, one of the simplest electronic
devices. This was achieved in two ways. The first way was to physically cross a p-type wire
over an n-type wire. The second method involved chemically doping a single wire with
different dopants along the length. This method created a p-n junction with only one wire.
After p-n junctions were built with nanowires, the next logical step was to build logic
gates. By connecting several p-n junctions together, researchers have been able to create the
basis of all logic circuits: the AND, OR, and NOT gates have all been built from
semiconductor nanowire crossings. It is possible that semiconductor nanowire crossings will
be important to the future of digital computing. Though there are other uses for nanowires
beyond these, the only ones that actually take advantage of physics in the nanometer regime
are electronic.
Nanowires are being studied for use as photon ballistic waveguides as interconnects
in quantum dot/quantum effect well photon logic arrays. Photons travel inside the tube,
electrons travel on the outside shell.When two nanowires acting as photon waveguides cross
each other the juncture acts as a quantum dot.
Conducting nanowires offer the possibility of connecting molecular-scale entities in a

molecular computer. Dispersions of conducting nanowires in different polymers are being
investigated for use as transparent electrodes for flexible flat-screen displays.
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Because of their high Young's moduli, their use in mechanically enhancing
composites is being investigated. Because nanowires appear in bundles, they may be used as
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tribological additives to improve friction characteristics and reliability of electronic
transducers and actuators. Because of their high aspect ratio, nanowires are also uniquely

suited to dielectrophoretic manipulation.
10
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Nano Wire Full Report

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Seminar Report 2011-2012 Nanowire batteries for next generation

Detailed morphology and structure characterization have shown that these

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Figure 1. Schematic of morphological changes that occur in Si duringelectrochemical

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Figure 3c.Transmission electron microscope image of a pristine SiNW with a partial Ni

We have developed a CMOS compatible process to fabricate SiNW battery electrodes

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Figure 4. Schematic representation of the fabrication of Si

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ADVANTAGES OF THE NANOWIRE BATTERY

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Dr. Yi Cui, Assistant Professor of Material Science and Engineering