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11 Lithium Ion Batteries and Supercapacitors

11 Lithium Ion Batteries and Supercapacitors

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Nanochemistry



Fig. 10.43 A lithium-ion battery with a carbon nanotube cathode grown on a silicon substrate

and cellulose infiltrated with the electrolyte. Electricity is produced when lithium on the anode is

oxidized to form lithium ions, which are inserted into the nanotube cathode. Charging occurs when

the lithium ions move in the opposite direction and are deposited as lithium metal on the anode.

(Reprinted with permission from [10.112]. © 2007 Nature Publishing Group)



capacity of Sn in the composite electrode is calculated to be 0.96 Ahg−1 , which

is 96.9% of the theoretical capacity (0.99 Ahg−1 ) [10.115].



10.11.3 LiFePO4 Cathodes

Electrodes made of LiFePO4 nanoparticles (40 nm) [10.116, 10.109] formed

by a low-temperature precipitation process (Fig. 10.45) exhibit sloping voltage

charge/discharge curves, characteristic of a single-phase behavior. The presence



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Lithium Ion Batteries and Supercapacitors



521



Fig. 10.44 Transmission

electron micrograph (TEM)

of a nanostructured tin–cobalt

anode showing nanoparticles

of ∼6 nm diameter embedded

in a carbon matrix. (Reprinted

with permission from

[10.113]. © 2000 Elsevier)



Fig. 10.45 Characterization of a 40 nm nanosized LiFePO4 sample. (a) Scanning electron micrograph of the LiFePO4 nanocrystallites. (b) High-resolution transmission electron micrograph of a

crystallite combined with the Fourier transform of one box showing the orientation of the crystallite. (Reprinted with permission from referecne [10.109]. © 2008 Nature Publishing Group)



of defects and cation vacancies, as deduced by chemical/physical analytical techniques, is crucial for the properties [10.109]. Ultrahigh discharge rates with a

rate capability equivalent to full battery discharge in 10–20 s can be achieved

[10.117] by preparing a glassy lithium phosphate coating on the surface of nanoscale

LiFePO4 (see Fig. 10.46). These discharge rates are comparable to those of

supercapacitors (see below), which, however, trade high power for low energy

density.



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Fig. 10.46 Transmission electron microscopy (TEM) of a LiFePO4 nanocrystallite coated with

glassy lithium phosphate [10.117, 10.118]. (Reprinted with permission from [10.118]. © 2009

Elsevier)



10.11.4 Supercapacitors

It is thought that the energy and power for electronic devices cannot only be supplied

by batteries but also by supercapacitors. In such a supercapacitor, carbon nanotube

networks can comprise both the electrodes and the charge collectors [10.119] and

are spray coated onto a plastic substrate from solution. A gel electrolyte is used, as

it enables all components of the supercapacitor to be realized using printable materials. The energy and power densities of this device were measured at 6 Wh/kg and

23 kW/kg, respectively, which are comparable to values of commercially available

devices, despite the use of printable materials.



10.12 Environmental Nanotechnology

In 1989, the Exxon Valdez ran aground in Alaska, releasing 11 million US gallons of crude oil and killing approximately 250,000 seabirds, seaotters, and eagles.

This incident emphasized the need for materials that can effectively separate oil and

water for cleaning up oil spills. Certain properties of nanomaterials – such as high

surface-to-volume ratios and our ability to make surfaces that are either hydrophilic

or hydrophobic – may provide solutions to this problem [10.120, 10.121].

Potassium manganese oxide nanowires each about 20 nm in diameter assemble

into bundles that can be hundreds of micrometers long (Fig. 10.47a), resulting in



10.12



Environmental Nanotechnology



523



Fig. 10.47 The properties of nanomaterials make them ideal candidates for use in oil/water separation [10.120]. (a) The mesh of potassium manganese oxide nanowires provides a porous structure

with high surface-to-volume ratio and is shown with increasing magnification from left to right

[10.120]. (b) The contact angle, θ, quantifies the wetting behavior of a material. (c) The membrane

surface displays heterogeneous wetting when in contact with water (left) but homogeneous wetting for oil (right) [10.121]. (Reprinted with permission from [10.121]. © 2008 Nature Publishing

Group)



a membrane with a thickness of about 50 μm and an average pore size of about

10 nm, that causes a liquid to be sucked into the membrane by capillary action.

Materials with contact angles θ (Fig. 10.47b) smaller than 90◦ are more hydrophilic,

whereas those with contact angles above 90◦ are more hydrophobic (see Sect. 7.7).

Superhydrophobic surfaces (see [10.121]) cause water droplets to freely roll off –

like the self-cleaning properties of the lotus leaf (see Sect. 11.9). This is exactly what

happens for water with the potassium manganese oxide nanowire membranes modified with a hydrophobic coating [10.120] (Fig. 10.47c, left). However, if a liquid

that is less polar than water, such as oil, comes into contact with the surface, it will

be drawn into the interstitial space, where it rapidly replaces the air (Fig. 10.47c,



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right). This surface that repels water while allowing oil to selectively spread gives

rise to an extraordinary selectivity and capacity for the separation of oil from water –

the reported uptake capacities are as high as 20 times the initial weight of the nanomaterial. The membrane material exhibits a number of advantages, including its

high-temperature stability and the ease with which it can be recycled and reused,

confirming the potential of nanomaterials for protecting the environment [10.121].



10.13 Summary

Chemistry plays an important role in the bottom-up synthesis of nanostructures. By

means of supramolecular chemistry or the formation of inorganic hollow clusters,

nanometer-sized species can be fabricated conveniently. Chemical processes can be

investigated on the nanoscale by using scanning probe microscopy-based techniques

for manipulation and delivery of single molecules in a precisely controlled manner.

In heterogeneous catalysis, where the reacting molecules are absorbed on catalytically active solid surfaces, experimental studies down to the atomic level are most

successful in combination with ab initio calculations. Evidently, nanoscience may

have an impact on future energy problems, in particular in the field of renewable

energy such as solar energy (photovoltaics and thermal conversion), conversion of

mechanical energy into electricity, fuel cells or energy storage by lithium ion batteries, supercapacitors, or hydrogen storage devices. For environmental protection

strategies, nanostructures may be an optimum choice.



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Nanochemistry



Chapter 11



Biology on the Nanoscale



Nanoscience plays an important role in the study of biological phenomena because

the size of inorganic nanoparticles as probes and the spatial resolution of nanotools

match the sizes of macromolecular components employed in living systems.

Proteins, nucleic acid fragments, and their supramolecular complexes involved in

the DNA replication and transcription, and the ribosome, have typical dimensions

in the range of 2–200 nm.

An other interesting aspect is that the sizes of the physical world, that can be

explored and controlled nowadays by nanotechnology will become very close to the

sizes where the physicochemical bases and limits of living processes lie [11.1]. The

orderliness necessary for the set of processes which characterize the living state can

only be maintained against fluctuations in a system of a certain degree of complexity and, therefore, of a minimum size. However, what is the limiting value of this

complexity? It has been shown [11.2] that, for spatio-temporal self-organization,

the sizes as well as the dimensionality of the system are essential parameters. One

model of the first living system to arise on Earth [11.3] yields a minimum value of

about 6 × 106 atoms making up such a living system. This corresponds to a size of

about 40–50 nm which is within the range of the size of a virus (30–500 nm) or of

small biological structures (see Fig. 11.1).

In addition, nanoparticles of inorganic materials are essential building blocks

in biomineralization, a fundamental biological process in which nature chemically

generates morphology by means of genetic instructions.

The present section will start with a brief overview of the structure of the

cell and a subsequent subsection on nanoparticles for bioanalysis. Then recent

developments of biological nanomechanics will be reported. After a review of

the structure of molecular motors and of membrane channels, some features of

biomimetics and of the structure of bone and teeth will be outlined. Finally

nanostructures in biophotonics, the lotus effect, in food and in cosmetics will be

described.



H.-E. Schaefer, Nanoscience, DOI 10.1007/978-3-642-10559-3_11,

C Springer-Verlag Berlin Heidelberg 2010



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Fig. 11.1 Nanosized biological objects. (a) Human herpes virus 3; scale bar 100 nm.

(b) Enterobacteria phage; scale bar, 50 nm. (c) Intestinal villi (fine, hair-like epidermal outgrows), diameter ∼100 nm [11.4]. (Reprinted with permission from [11.4] (a) (b) and Dennis

Kunkel Microscopy (c). © 2009 Nature Publishing Group (a) (b) and © 2009 Dennis Kunkel

Microscopy (c))



11.1 The Cell – Nanosized Components, Mechanics, and Diseases

Understanding of cells – that is understanding of life – is one of the great unanswered questions of science. The cell is the quantum of biology and the smallest

and most fundamental unit. The cell contains a system of molecules and nanoscale

machines, i.e., functional molecular aggregates of great complexity. Understanding

the molecular nanostructures will help us to move closer to understanding human

life and health, and thus toward “nanomedicine” [11.5].



11.1



The Cell – Nanosized Components, Mechanics, and Diseases



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11.1.1 Cell Structure

Most of the biological cells are 1–100 μm in size and they comprise many nanosized

constituents (Fig. 11.2). Structural studies with nanoscale resolution can be performed by cryoelectron microscopy [11.7] (see Sect. 2.6), by electron microscopy

[11.13] of whole cells in liquid [11.8], or by far-field stimulated emission depletion (STED) optical microscopy [11.9, 11.14] (see Sect. 2.4). The interior of the

cell (Fig. 11.2) includes the cytoplasm and the nucleus which contains the chromosomes with the DNA strands carrying the genes and functions in the transmission

of hereditary information. The cytoplasm contains the cytosol which is the “fluid”

in the cell, the endoplasmic reticulum, microtubules, actin filaments, intermediate

filaments, mitochondria, and the Golgi apparatus. The actin filaments (ca. 8 nm in

diameter; see Fig. 11.3a) and the microtubules, in the shape of hollow tubes with

a diameter of ca. 25 nm, form the cytoskeleton. The ribosomes found in the cytoplasm with a diameter of ca. 25 nm (see Fig. 11.3a, b) are minute round particles

composed of RNA and protein which are active in the synthesis of proteins. The

ribonucleoprotein of the ribosome represents the last step of the gene expression



Fig. 11.2 (a) Schematic diagram of a typical eukaryotic cell which contains many nanoscale elements (see text). (b) The phospholipid bilayer membrane which covers the cell. (Reprinted with

permission from [11.6]. © 2003 Nature Publishing Group)



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