Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

INTRODUCTION
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 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 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 Ge 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. Dept. of AEI IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

Often times, this leads to material losing electronic contact to the current collector 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 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. 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

RESULTS
Li insertion into the SiNWs was found to exhibit higher capacities than other forms 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 (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 Dept. of AEI IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 Nanowire batteries for next generation electronics 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 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 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.

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. Dept. of AEI IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

Figure 3c.Transmission electron microscope image of a pristine SiNW with a partial Ni coating before and after Li cycling.

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 Dept. of AEI IESCE

Seminar Report 2011-2012 Nanowire batteries for next generation electronics 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 vertical nanopillars with controllable diameters and spacings from 50nm to 1000nm. We have exploited these NW pillars as well-defined anodes for lithium batteries.

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 Dept. of AEI IESCE

Seminar Report 2011-2012 Nanowire batteries for next generation electronics reversibility and cyclability (Fig. 5). The nanorods performed significantly better than commercially available powders with particle sizes around 10 m at the higher rates.

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 m).

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

CONCLUSIONS
We have found that Si and Ge nanowires can perform as suitable high capacity 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

ADVANTAGES OF THE NANOWIRE BATTERY

Many advantages arise with the use of the silicon nanowire battery. This battery can 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 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

DISADVANTAGES OF THE NANOWIRE BATTERY

As with every new product, there are several disadvantages to the new silicon nanowire battery; car companies will have to design new cars, products operating on lithiumion 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 consumers 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

THE SILICON NANOWIRE BATTERY

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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

WHAT CAN THE NANOWIRE BATTERY REPLACE?

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 laptops battery life will last ten times longer; hence the battery life will be extended to twenty hours! The lithium-ion batterys anode, usually made with carbon material, has a limited 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

DESIGN
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. 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

POTENTIAL PROBLEM
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 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 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 formedexcept 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 ICLfor 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

NANOWIRE
A nanowire is a nanostructure, with the diameter of the order of a nanometer (109 meters). Alternatively, nanowires can be defined as structures that have a thickness 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.

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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IESCE

Seminar Report 2011-2012 Nanowire batteries for next generation electronics 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. Other important examples are based on semiconductors such as InP, Si, GaN, etc., dielectrics (e.g. SiO2,TiO2), or metals (e.g. Ni, Pt). 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

SYNTHESIS OF NANOWIRES

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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

USES OF NANOWIRES
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. 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.

Dept. of AEI

IESCE

Seminar Report 2011-2012 electronics

Nanowire batteries for next generation

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 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.

Dept. of AEI

IESCE