If you are typical of what constitutes a "journalist" today, no fucking wonder the public are science idiots.
Nature Nanotechnology 3, 31 - 35 (2008)
Published online: 16 December 2007 | doi:10.1038/nnano.2007.411
Subject Category: Electronic properties and devices
High-performance lithium battery anodes using silicon nanowires
Candace K. Chan1, Hailin Peng2, Gao Liu3, Kevin McIlwrath4, Xiao Feng Zhang4, Robert A. Huggins2 & Yi Cui2
Abstract
There is great interest in developing rechargeable lithium batteries with higher energy capacity and longer cycle life for applications in portable electronic devices, electric vehicles and implantable medical devices1. Silicon is an attractive anode material for lithium batteries because it has a low discharge potential and the highest known theoretical charge capacity (4,200 mAh g-1; ref. 2). Although this is more than ten times higher than existing graphite anodes and much larger than various nitride and oxide materials3, 4, silicon anodes have limited applications5 because silicon's volume changes by 400% upon insertion and extraction of lithium which results in pulverization and capacity fading2. Here, we show that silicon nanowire battery electrodes circumvent these issues as they can accommodate large strain without pulverization, provide good electronic contact and conduction, and display short lithium insertion distances. We achieved the theoretical charge capacity for silicon anodes and maintained a discharge capacity close to 75% of this maximum, with little fading during cycling.
Some might be interested in the patent. Sorry for the length, but I don't have a link only the downloaded PDF.
Patent title: Nanowire Battery Methods and Arrangements
Inventors: Yi Cui Candace K. Chan
Agents: CRAWFORD MAUNU PLLC
Assignees:
Origin: ST. PAUL, MN US
IPC8 Class: AH01M436FI
USPC Class: 42923195
Abstract: A variety of methods and apparatus are implemented in connection with a battery. According to one such arrangement,
an apparatus is provided for use in a battery in which ions are moved. The apparatus comprises a substrate and a
plurality of growth-rooted nanowires. The growth-rooted nanowires extend from the substrate to interact with the ions.
Claims: 1. An apparatus for use in a battery in which ions are moved, comprising:a substrate; anda plurality of nanowires, each
being growth-rooted from the substrate and having an outer surface with molecules that interact with the ions.
2. The apparatus of claim 1, further comprising first and second current collectors, wherein one of the current collectors
includes the substrate and the nanowires.
3. The apparatus of claim 2, further comprising a lithium-based ion transporter located between the current collectors.
4. The apparatus of claim 3, wherein the lithium-based ion transporter provides lithium ions for radial diffusion into the
nanowires.
5. The apparatus of claim 1, wherein the nanowires include silicon.
6. The apparatus of claim 4, wherein the nanowires are sufficiently small that they transport electrons in only one
dimension.
7. The apparatus of claim 1, wherein the nanowires have an average outer diameter in a range from 10 to 100
nanometers.
8. The apparatus of claim 1, wherein the nanowires include crystalline-state structures.
9. The apparatus of claim 1, wherein the nanowires include amorphous-state structures.
10. The apparatus of claim 1, wherein the nanowires do not include carbon nanotubes.
11. The apparatus of claim 1, further comprising an ion transporter and first and second current collectors located on
either side of the ion transporter, wherein one of the current collectors functions as part of the anode of the battery and
includes the substrate and the nanowires.
12. The apparatus of claim 11, wherein the ions and the nanowires are composed of first and second materials,
respectively, that are different from one another, and wherein the nanowires include alloy structures formed from the
first and second materials and formed during cycling of the battery.
13. The apparatus of claim 12, wherein the ions include Lithium ions and the nanowires include Silicon, and wherein
the alloy structures include Lithium and Silicon.
14. A battery having a stable energy capacity, comprising:an ion transporter to transport ions;a first current collector on
one side of the ion transporter; anda second current collector, located on another side of the ion transporter, including a
substrate and a plurality of solid nanowires that are growth-rooted from the substrate and that interact with the ions to
set the stable energy capacity greater than about 2000 mAh/g.
15. A battery that is recharged, comprising:an ion transporter to transport ions;a first current collector on one side of the
ion transporter; anda second current collector, located on another side of the ion transporter, including a substrate and
a plurality of solid nanowires that are growth-rooted from the substrate and that interact with the ions to set a maximum
capacitive fading between subsequent battery cycling at less than about 25 percent.
16. The battery of claim 15, wherein, in a discharge state, the solid nanowires are one of Si, Ge and Sn.
17. The battery of claim 15, wherein, in a discharge state, the solid nanowires include an alloy of one of Si, Ge and Sn
and of another material.
18. The battery of claim 15, wherein substantially all of the solid nanowires are directly connected to the substrate.
19. The battery of claim 15, wherein, in a charge state, the solid nanowires have amorphous portions that include an
alloy formed from the combination of the solid nanowires and the ions.
20. A battery having an energy capacity, comprising:a first current collector having a substrate;a second current
collector;an ion transporter located between the first and second current collectors, the ion transporter providing ions;
anda layer of nanowires having a layer height equal to the length of about one of the nanowires, the layer of nanowires
including nanowires extending from the substrate toward the ion transporter to combine with ions from the ion
transporter, and setting the energy capacity for the battery.
21. The battery of claim 20, wherein the nanowires include a material chemically bound to the substrate and wherein
the energy capacity for the battery is greater than about 2000 mAh/g.
22. The battery of claim 20, wherein the nanowires are solid and growth-rooted from the substrate and are not carbon
nanotubes.
23. The battery of claim 20, wherein, in a discharge state, the nanowires are one of Si, Ge and Sn.
24. The battery of claim 20, wherein, in a discharge state, the nanowires include an alloy of one of Si, Ge or Sn and
another material.
25. The battery of claim 20, wherein the first current collector is an anodal current collector and the second current
collector is a cathodal current collector.
26. The battery of claim 25, wherein the energy capacity for the battery is less than about 2000 mAh/g.
27. The battery of claim 20, wherein substantially all of the nanowires are directly connected to the substrate.
28. The battery of claim 20, wherein a majority of the nanowires have an angle greater than about 60 degrees from the
end located on the substrate and a second end, the angle being such that 90 degrees is perpendicular to a surface of
the substrate at which the first end is located.
29. The battery of claim 20, wherein the nanowires include one of a metal oxide and a metal nitride.
30. A battery, comprising:a first current collector;a second current collector;an ion transporter located between the first
and second current collectors and one of the collectors including a substrate; andsolid nanowires to combine with ions
provided by the ion transporter for defining the nominal energy capacity, wherein a preponderance of the solid
nanowires are located on the substrate and have an end located on the substrate.
31. The battery of claim 30, wherein the battery has a nominal energy capacity that is defined as a function of the solid
nanowires that combine with ions provided by the ion transporter and of the ability of the solid nanowires to deliver
power to the substrate.
32. The battery of claim 30, wherein the solid nanowires provide an average energy capacity of greater than about
2000 mAh/g.
33. The battery of claim 30, wherein a majority of the solid nanowires have an angle greater than about 60 degrees
from the end located on the substrate and a second end, the angle being such that 90 degrees is perpendicular to a
surface of the substrate at which the first end is located.
34.-37. (canceled)
38. The apparatus of claim 14, wherein the nanowires have an average outer diameter that is greater than 50
nanometers.
39. The battery of claim 14, wherein the nanowires have an average outer diameter that is less than 300 nanometers.
40. The battery of claim 15, wherein the nanowires have an average outer diameter in a range from 50 to 300 nanometers.
41. A battery having a stable energy capacity, comprising:an ion transporter to transport ions;a substrate;a first current collector on one side of the ion transporter; anda second current collector, located on another side of the ion transporter, including the substrate and a plurality of solid nanowires that are growth-rooted from the substrate and that interact with the ions to set the stable energy capacity greater than about 2000 mAh/g, and each of the plurality of nanowires having an outer surface with molecules that interact with the ions.
Description:
FIELD OF THE INVENTION
<0001>The present invention relates generally to ion battery arrangement and methods, and more particularly to nanowire-based electrode arrangements and approaches involving the assembly or manufacture of nanowire electrode arrangements.
BACKGROUND
<0002>The demand for batteries with high energy capacity, low weight and long lifetime has become increasingly important in a variety of fields and industries, including those relating to portable electronic devices, electric vehicles, and implantable medical devices. For example, the energy capacity, weight and cycle life characteristics are often useful for improving the functionality of a particular device in which the batteries are used. In portable electronic devices and implantable medical devices, these and other related aspects are useful to allow for increases in power (e.g., from additional processing power) and/or reduction in the size of the devices. In electric vehicles, these aspects are often limiting factors in the speed, power and operational range of the electric vehicles.
<0003>Various commercial embodiments of batteries function as an electrochemical cell that stores and converts chemical energy from chemical oxidation and reduction reactions into a useable electrical form. The chemical reactions occur in the materials composing the two electrodes of the battery, such as reduction occurring in the cathode and oxidation occurring in the anode. These reactions are due in part to a difference in electrochemical potential between the materials comprising the anode and cathode. In many ion-based batteries, the two materials electrodes are separated by an ionic conductor, such as an electrolyte, that is otherwise electrically insulating. Each electrode material is electrically connected to an electronically conducting, preferably metallic, material sometimes called the current collector. The current collectors can then be connected to one another using an external circuit that allows for electron transfer therebetween. To equalize the potential difference, the anode releases ions (e.g., by oxidizing to form the ions) when electrons are allowed to flow through the external circuit. The flow of electrons is balanced by the flow of ions through the electrolyte. The ions then react with the chemically reactive material of the cathode. The number of ions that a material can accept is known as the specific capacity of that material. Battery electrode materials are often defined in terms of the energy capacity per weight, for example in mAh/g. Much research has been devoted to creating and developing higher energy density electrode materials for higher capacity batteries.
<0004>A specific type of battery is a Lithium-ion battery, or Li-ion battery. Li-ion batteries transport Li ions between electrodes to effect charge and discharge states in the battery. One type of electrode uses graphite as the anode. Graphite anodes have reversible (rechargeable) capacities that are on the order of 372 mAh/g. Graphite anodes function by intercalation of Li ions between the layered-structure. A limitation in some graphitic anodes is that Li is saturated in graphite at the LiC6 stoichiometry. Materials that can allow for larger amounts of Li insertion, therefore, have been attractive for use as high capacity Li battery anodes.
<0005>Some alternatives to graphite anodes utilize storage mechanisms that do not involve the intercalation of Li ions between layered-structure materials. For example, some transition metal oxides use a conversion mechanism that can provide relatively high energy anodes of 700 mAh/g. Other alternatives include elements, such as Si, Sn, Bi, and Al, which form alloys with Li through Li insertion. Some of these elements provide relatively large theoretical energy capacities. Often such elements exhibit a volume change during Li insertion. For example, pure Si has a theoretical capacity of 4200 mAh/g for Li4 4Si, but has been shown to produce as much as a 400% volume change during Li insertion (alloying). In films and micron-sized particles, such volume changes may cause the Si to pulverize and lose contact with the current collector, resulting in capacity fading and short battery lifetime. Electrodes made of thin amorphous Si may exhibit improvements in capacity stability over many cycles, but such films seldom have enough active material for a viable battery. Attempts to increase conductivity using conducting carbon additives have not completely solved such problems, since upon dealloying (delithiation), the particles may contract, and thereby, lose contact with the carbon. Si anodes have been prepared with a polymer binder such as poly(vinylidene fluoride) (PVDF) to attempt to hold the particles together, but the elasticity properties of PVDF may not be sufficient for the large Si volume change and do not completely mitigate the poor conductivity. This results in a low coulombic efficiency and poor cyclability. For example, the use of 10 μm sized Si particles mixed with carbon black and PVDF has been shown to result in a first discharge capacity of 3260 mAh/g; however, the charge capacity is only 1170 mAh/g, indicating a poor coulombic efficiency of only 35%. After 10 cycles, the capacity also faded to 94%. Moreover, conductive additives and binders add weight to the electrode, lowering the overall gravimetric and volumetric capacities of the battery.
<0006>These and other characteristics have been challenging to the design, manufacture and use of Li-alloy materials in Li-battery anodes. A solution has been to use nanostructure battery electrode materials. Nanomaterials include nanowires, nanoparticles, and nanotubes, all of which have at least one dimension in the nanometer dimension. Nanomaterials have been of interest for use in Li batteries because they have better accommodation of strain, higher interfacial contact area with the electrolyte, and short path lengths for electron transport. These characteristics may lead to improved cyclability, higher power rates, and improved capacity. Current efforts, however, leave room for improvement.
SUMMARY OF THE INVENTION
<0007>The present invention is directed to overcoming the above-mentioned challenges and others related to the types of applications discussed above and in other applications. These and other aspects of the present invention are exemplified in a number of illustrated implementations and applications, some of which are shown in the figures and characterized in the claims section that follows.
<0008>According to one example embodiment, an apparatus is provided for use in a battery. The apparatus provides high energy capacity through the novel use of nanowires that alloy with the ions. A specific example of the apparatus employs nanowires constructed from materials other than carbon to alloy with Li.sup.+ ions during a charge state of the battery and to release the Li.sup.+ ions during a discharge state. Careful growth of the nanowires directly from the substrate, which is connected to the current collector, can provide an apparatus having nanowires that are substantially all directly connected to the substrate and that extend therefrom.
<0009>According to another embodiment, an apparatus is provided for use in a battery in which ions are moved. The apparatus comprises a substrate and a plurality of nanowires, each being growth-rooted from the substrate and each having an outer surface with molecules that interact with the ions.
<0010>According to another embodiment of the invention, a battery is provided that has a stable energy capacity. The battery comprises an ion transporter to provide ions; a first current collector on one side of the ion transporter; and a second current collector, located on another side of the ion transporter. The second current collector includes a substrate and a plurality of solid nanowires that are growth-rooted from the substrate and that interact with the ions to set the stable energy capacity greater than about 2000 mAh/g.
<0011>According to another embodiment of the invention, a battery that is recharged is provided. The battery comprises an ion transporter to provide ions, a first current collector on one side of the ion transporter and a second current collector that is located on another side of the ion transporter and that includes a substrate and a plurality of solid nanowires. The solid nanowires are growth-rooted from the substrate and interact with the ions to set a maximum capacitive fading between subsequent energy charges at less than about 25 percent.
<0012>According to another embodiment of the invention, a battery is provided that has an energy capacity. The battery comprises a first current collector having a substrate, a second current collector, an ion transporter located between the first and second current collectors, the ion transporter providing ions, and a layer of nanowires. The layer of nanowires has a layer height equal to the length of about one of the nanowires. The layer of nanowires also includes nanowires that extend from the substrate toward the ion transporter to combine with ions from the ion transporter and that set the energy capacity for the battery.
<0013>According to another embodiment of the invention, a battery is provided. The battery comprises a first current collector, a second current collector, an ion transporter located between the first and second current collectors and one of the collectors including a substrate, and solid nanowires to combine with ions provided by the ion transporter for defining the nominal energy capacity. A preponderance of the solid nanowires are located on the substrate and have an end located on the substrate.
<0014>According to another embodiment of the invention, a method of an electrode arrangement that has a substrate for connecting to a current collector is implemented. The electrode arrangement is designed for use in a battery. The method comprises the step of growing solid nanowires from the substrate.
<0015>According to another embodiment of the invention, a method is implemented for assembling an electrode arrangement for use in a battery. The method comprises attaching a substrate with growth-rooted solid nanowires to a current collector, forming a current collector assembly with an ion transporter located between the substrate and current collector and another current collector; and placing the current collector assembly within a housing.
<0016>The above summary is not intended to describe each illustrated embodiment or every implementation of the present invention.