Historical overviews

In this chapter, attention is focused on the technology of the hthium batteries. After a brief historical overview, we draw most of the primary and secondary lithium batteries. To get further information on the interest of these power sources, we invite the readers to consult works in references as there have been pubhshed numerous excellent books on LiBs based on various different viewpoints [3-16]. However, there are few books available on the state-of-the-art and future of next generation LiBs, particularly eventually for EVs and HE Vs. 

Research in lithium batteries began in 1912 under GJS[. Lewis, but the breakthrough came in 1958 when Harris noticed the stabihty of Li-metal in a number of nonaqueous (aprotic) electrolytes such as fused salts, hquid SO2, or hthium salt into an organic solvent such as LiC104 in propylene carbonate (C4H6O3). The formation of a passivation layer that prevents the direct chemical reactimi between hthium metal and the electrolyte but stih allows for ionic transport is at the origin of the stabihty of hthium batteries [17]. 

These researches opened the door to the fabrication and commercialization of varieties of primary hthium batteries since the late l%0s nonaqueous hthium cells, especially the 3-V primary systems, have been developed. These systems include lithium-sulfur dioxide (Li//S02) cehs, lithium-polycarbon monofluoride (Li//(CF t) ) cells introduced by Matsuschita in 1973, lithium-manganese oxide (Li//Mn02) cells commercialized by Sanyo in 1975, lithium-copper oxide (Li//CuO) cells, lithium-iodine (Li//(P2VP)1J cells. During the same period, molten salt systems (LiCl-KCl eutecticum) using a Li-Al alloy anode and a FeS cathode were introduced [1]. The lithium-iodine battery has been used to power more than four million cardiac pacemakers since its introduction in 1972. During this time the lithium-iodine system has established a record of reliability and performance unsurpassed by any other electrochemical power source [18]. 

In the early 1970s was discovered the reversible insertion of guest species (ions, organic molecules, organometalhcs) into an host lattice that maintains its structural features but exhibits new physical properties. The first work was initiated by 

Battery Potential (V) Specific energy (Wh kg ) Company/year 

Theoretical developments have kept pace with or surpassed developments in the experimental side of VCD. Since the earliest theory developed by 

The correct structure of this compound, which was predicted by Wolfrom et al.,w was subsequently confirmed by X-ray crystallography.19 Nevertheless, this mistaken identification has been quoted in the literature as late20 as 1990. A crystal structure of a-D-Fru/-l,2 2,3 -p-D-Fru/(6) has also been published.21 

In 1952, Wolfrom and Hilton demonstrated that L-sorbose was also capable of forming dimeric dianhydrides,22 and they postulated sorbofuranosyl and pyra-nosyl cationic intermediates. In 1955, Boggs and Smith23 postulated a fructofu-ranosyl cationic intermediate in the formation of per-O-acetyl ot-D-Fru/-1,2 2,l -p-D-Fru/[di-D-fructose anhydride I (5)] from inulin triacetate. They indicated that three adjacent P-2,l -linked fructofuranosyl units would be required for formation of the dianhydride. 

The introduction in 1965 by Kohn and Sham7 of a practical computational scheme may, therefore, be considered to be the next major milestone in the development of formal DFT. The essential ingredient in this approach is the postulation of a reference system of N noninteracting electrons, moving in an effective external potential vs(r), the so-called Kohn-Sham potential, instead of the electrostatic potential v(r) of the nuclei  

The first term in brackets is the usual kinetic energy operator. The noninteracting reference system has the property that its one-determinantal wavefunction of the lowest N orbitals yields the exact density of the interacting system with external potential v(r) as a sum over densities of the occupied orbitals, that is, p(r) = Xl ) ,l2, and the corresponding exact energy E[p(r)]. The Kohn-Sham potential should account for all effects stemming from the electron-nuclear and electron-electron interactions. Not only does the Kohn-Sham potential contain the attractive potential v(r) of the nuclei and the classical Coulomb repulsion VCoul(r) within the electron density p(r), but it also accounts for all exchange and correlation effects, which have so to say been folded into a local potential vxc r)  

Stable triply-bonded compounds with group 14 elements are still unknown. Several formally triply-bonded silicon compounds were detected and characterized in matrix and 

Although inherently incomplete, it is of interest to review briefly some of the most important theoretical aspects of luminescence. In general it can be stated, that most of the processes, leading to luminescence, are understood well nowadays. A very 

For instance, the efficiency of luminescent materials is not determined well. Only in the case of excitation with high-energy radiation (e.g. cathode rays), can the maximum energy efficiency be calculated rather accurately, using a surprisingly simple treatment [5.225]. In contrast, loss processes (which do not result in luminescence) cannot yet be predicted well quantitatively. 

Today the most important producers of luminescent pigments are Honeywell and Nemoto. 

The absorption of energy, which is used to excite the luminescence, takes place by either the host lattice or by intentionally doped impurities. Moreover, the excitation energy can be transferred through the lattice by a process called energy transfer. In most cases, the emission takes place on the impurity ions. Quite frequently, the emission color can be adjusted by choosing the proper impurity ion, without changing the host lattice in which the impurity ions are incorporated. 

In the case of center luminescence, the emission is generated on an optical center, in contrast to e.g. emission which results from optical transitions between host lattice band states. Such a center can be an ion or a molecular ion complex. 

In the classical era in Europe, the theory and practice of chemistry were pursued mainly by the ancient Greeks, who made many important discoveries in metallurgy in particular and who are also credited with proposing the earliest version of the atomic theory. The Greek chemical tradition declined when mysticism displaced the observational approach in the second century of the Common Era, and subsequently was largely lost in Europe after the fall of Rome in 410 C.E. In the 11th. century c.e., the quasiscience of alchemy returned to Europe via the Arabs, who also introduced Persian, Indian, and Chinese influences. 

Alchemy fell into disrepute in Europe in the Middle Ages because of its obscure symbolism, introduction of irrelevant religious ideas and superstitions, and preoccupation with perfectibility that led to belief in the possibility of the transmutation of metals (as opposed to chemical change). The prospect of changing base metals such as lead into gold attracted all 

In the early 1900s, the work of Volta, Berzelius, Davy, and Faraday on electrolysis (i.e., splitting a chemical compound into its constituents by passage of an electrical current, e.g., splitting water into hydrogen and oxygen gases or molten common salt into metallic sodium and chlorine gas) 

it is recognized that an atomic nucleus consists of a number of protons (particles of charge number H- and mass number approximately 1) and neutrons (chargeless particles of mass number approximately 1) bound together by a short-range force known as the strong force. The total charge number is then the atomic number, and the total mass number (which is less than the sums of the mass numbers of the free constituent particles by a 

The periodicity of chemical properties arises from filling of successive quantum mechanical shells of electrons. For example, filling of the s,p shells, with capacities of 8 electrons each, and the d shells, which can hold up to 10 electrons, is associated with the main group and transition elements, respectively (Fig. 1.1). Before the advent of quantum theory, two classes of elements were known that seemed not to fit the Mendeleyevian scheme an uncertain number of rare earth elements or lanthanides— metallic elements, discovered throughout the 1800s, that form oxides of 

Beginning in 1985, a series of patents was issued for the use of ibogaine as a rapid means of interrupting addiction to narcotics (morphine and heroin) (3), cocaine and amphetamine (4), alcohol (5), nicotine (6) and polydrug dependency syndrome (35). These patents claim that an oral or rectal dose of ibogaine (4-25 mg/kg) interrupts the dependence syndrome, allowing patients to maintain a drug-free lifestyle for at least 6 months. 

In these early days, only quaternary phosphorus compounds were resolved. Ethylmethylphenylphosphine oxide (1) constitutes the first ever racemic F-stereogenic compound separated into individual enantiomers in 1911 by Meisenheimer and Lichtenstadt. It took 15 years for the same laboratory to repeat that feat and apply the same method to resolve benzylmethylphenyl-phosphine oxide (2). In 1944 sulfide 3 was resolved by Davies and Mann and 15 years later McEwen and co-workers resolved the first acyclic phosphonium salt (4). 

Those compounds were synthesised by alkaline hydrolysis or cathodic reduction of phosphonium salts or by reduction of phosphine oxides with silanes. In both cases, the optically pure precursor had to be prepared by chemical resolution (see Chapter 2, Section 2.2), a step that is time-consuming, inefficient and very dependent on the structure of the compound being resolved. 

Two key breakthroughs occurred in 1967-1968. The first one was the development of a new, relatively flexible route for the preparation of phosphine oxides, based on the separation of asymmetrically substituted menthylpho-sphinates. This method, described in Chapter 2, allowed the preparation of 

The optical yields of 9 were low, but proved that enantioselective catalytic homogeneous hydrogenation was feasible. The extremely low enantioselectivity with the phosphine of entry 5 (Table 1.1) was justified by the location of the stereogenic centres further away from the metal in comparison to P-stereogenic phosphines. 

At the same time, it was discovered that (5)-amino-3-(3,4-dihydroxyphenyl) propanoic acid (l-DOPA) was very efficient in the treatment of Parkinson s disease, thereby creating a sudden demand for this rare amino add. Knowles and co-workers, who were working at Monsanto, produced vanillin that was used in the synthesis of an l-DOPA precursor. They dedded to use the newly 

Normative ethics (Fig. 2.2) involves arriving at moral standards that regulate right and wrong conduct. The Golden Rule [21] is an example of such a moral standard. The key assumption in normative ethics is that there is only one ultimate criterion of moral conduct, whether it is a single rule or a set of principles. Three variations in normative ethics are (1) virtue theories, (2) duty theories, and (3) consequentialist theories [22]. 

Virtue ethics places less emphasis on learning rules, and instead stresses the importance of developing good habits of character. Historically, virtue theory is one of the oldest normative traditions in Western philosophy, having its roots in ancient Greek civilization. Plato emphasized four virtues in particular, which were later called cardinal virtues, wisdom, courage, temperance and justice. 

Duty theories base morality on specific, foundational principles of obligation. Two terms that are used to describe duty theories are deontological from the Greek word deon or duty and nonconsequentialist as these principles are 

FIGURE 2.5 Overview of ethics with connections to engineering codes 

After another devastating explosion in 1866 which completely destroyed the NG factory, Alfred Nobel focused on the safe handling of NG explosives. In order to reduce the sensitivity, Nobel mixed NG (75%) with an absorbent clay called Kieselguhr (25%). This mixture called Guhr Dynamite was patented in 1867. Despite the great success of dynamite in the civil sector, this formulation has never found significant application or use in the military sector. 

One of the great advantages of NG (Fig. 1.2) in comparison to blackpowder (75% KNO3, 10% Sg, 15% charcoal) is that it contains both the fuel and oxidizer 

Tetryl was developed at the end of the 19 century (Fig. 1.3) and represents the first explosive of the nitroamino (short nitramino) type. Tetryl is best obtained by dissolving monomethylaniline in sulfuric acid and then pouring the solution intro nitric acid, while cooling the process. 

The above mentioned disadvantages of PA are overcome by the introduction of trinitrotoluene (TNT). Pure 2,4,6-TNT was first prepared by Hepp (Fig. 1.3) and its structure was determined by Claus and Becker in 1883. In the early 20 century TNT almost completely replaced PA and became the standard explosive during WW I. TNT is produced by the nitration of toluene with mixed nitric and sulfuric acid. For military purposes TNT must be free of any isomer other than the 2,4,6- 

Nitroguanidine (NQ) was first prepared by Jousselin in 1887 (Fig. 1.3). However, during WW I and WW II it only found limited use, for example in formulations 

During the two decades that have passed since the above-described studies were conducted, the synthesis of nanomaterials has attracted enormous attenhon, and the synthesis of nanostructured zirconia has become a focus of research. Whereas, during the early days research into nanoscale particles was carried out mainly by those achve in the field of ceramics, today the major inveshgahons into nanostruc- 

The main advantage of the chemical solution-based methods used to prepare metal oxide nanoparticles is the excellent homogeneity of the resultant particles, even when a complex metal oxide system is the target rather than a pure oxide. Espe- 

The roots of iminium activation can be traced back to the pioneering works of Knoevenagel [4]. The Knoevenagel condensation became the first reaction that might proceed via iminium catalysis. Next, Pollack reported that several proteins and amino acids catalyzed the decarboxylation of acetoacetic acid. The mechanism suggested by Petersen involves an imine intermediate [5]. 

In 1937, Langenbeck reported the first iminium catalyzed conjugated addition. N-Methylglycine and piperidinium acetate were found to be good catalysts for the conjugate addition of water to crotonaldehyde [6]. 

Yamaguchi and coworkers reported in the early 1990s the use of alkali metal salts of proline (e.g., rubidium prolinate) for the conjugate addition of malo-nates to enals with promising results [8]. Soon after, Taguchi and coworker developed a similar reaction using (2-pyrroUdyl)(alkyl)ammonium hydroxide as catalyst [9]. 

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Vedam K 1998 Spectroscopic ellipsometry a historical overview Thin Solid Films 313/314 1-9... 

Schenk, G. Historical Overview of Fluorescence Analysis to 1980, Spectroscopy 1997,12, 47-56. 

Isbell, W.M. (1987), Historical Overview of Hypervelocity Impact Diagnostic Technology, Internat. J. Impact Engrg., 5, pp. 389-410. 

A variety of methods for finding reaction paths in simple chemical systems have been proposed. Good review articles summarizing those methods can be found [8,15,16]. An excellent historical overview of these methods is provided by Anderson [17]. Here we focus our discussion on those methods that have had the widest application to large-scale biomolecular systems and that hold the greatest promise for further development. 

A discussion of the motivation behind doing sputtered neutral analysis versus SIMS, plus a description of the first prototype SALI instrument. A well written introduction for someone without previous surface analysis experience it also includes an historical overview of the various post-ionization techniques. 

In an excellent historical overview of these stages and the intellectual and practical problems which had to be overcome, Mulvey (1995) remarks that the first production microscopes pursued exactly the same electron-optical design as Ruska s first experimental microscope. The stages of subsequent improvement are outlined by Mulvey, to whom the reader is referred for further details. 

The role of the Bell Labs metallurgists in the creation of the early transistors was clearly set out in a historical overview by the then director of the Materials Research Laboratory at Bell Labs, Scaflf (1970). 

According to an early historical overview (Jones 1960), the numerous attempts to understand the sintering process in both ceramics and metals fall into three periods (1) speculative, before 1937 (2) simple, 1937-1948 (3) complex, 1948 onwards. The complex experiments and theories began just at the time when metallurgy underwent its broad-based quantitative revolution (see Chapter 5). 

Cahn, R.W. (2000) Historical overview, in Multiscale Phenomena in Plasticity (NATO ASI) eds. Saada, G. et al. (Kluwer Academic Publishers, Dordrecht) p. 1. 

The developmental histories of artificial life and cellular automata have been intertwined ever since von Neumann hrst showed how to construct a self-reproducing automaton ([voiiN66] see section 11.7). A brief historical overview of artificial life appears in chapter 11. 

Aitken A (2006) 14-3-3 Proteins a historic overview. Semin Cancer Biol 16 162-172... 

Diheterolevulosans, 209-211, 240 Dihexulose dianhydrides, 207 -266, see also Caramels Di-D-fructose dianhydrides 13C NMR spectra, 245-246 conformation, electronic control, 224-228 conformational rigidity, energetic outcomes, 228 hexulopyranose rings, 226 historical overview, 210-213 H NMR spectra, 248 -249 intramolecular hydrogen-bonds, 227 isomerization, 231 -232 1,2-linked, ero-anomeric effect, 224-225 listing, 240-241 nomenclature, 208-210 optical rotations and melting points, 242-243 protonic activation... 

Trumper, R. (2003). The physics laboratory A historical overview and future perspectives. Science... 

Brief Historical Overview of P-Chirogenic Phosphine Ligands... 

An ELN may be viewed as an enterprise software application that enables scientists to record chemical and biological data and to search and share their work with their colleagues, who can be on the other side of the globe. This simplistic definition is not sufficient to portray what real-world ELN applications do and how they have improved the productivity of scientists, engineers, and innovators. Therefore, a historical overview is useful to help understand the broader usefulness of ELN applications. 

A. Historical Overview of Triatomic Rare Gas-Dihalogen Interactions... 

Schwerdtfeger, P. and Thierfelder, C. (2006) Relativistic Quantum Chemistry -A Historical Overview, in Trends and Perspectives in Modem Computational Science, Vol. 6 Lecture Series on Computer and Computational Sciences (eds G. Maroulis and T. Simos), Brill Academic Publishers, Leiden, The Netherlands, pp. 453-460. 

Hydrodynamic Techniques for Investigating Reaction Kinetics at Liquid-Liquid Interfaces Historical Overview and Recent Developments... 

In this chapter, we describe some of the more widely used and successful kinetic techniques involving controlled hydrodynamics. We briefly discuss the nature of mass transport associated with each method, and assess the attributes and drawbacks. While the application of hydrodynamic methods to liquid liquid interfaces has largely involved the study of spontaneous processes, several of these methods can be used to investigate electrochemical processes at polarized ITIES we consider these applications when appropriate. We aim to provide an historical overview of the field, but since some of the older techniques have been reviewed extensively [2,3,13], we emphasize the most recent developments and applications. 

During the Golden Age of Islam (7th through the 17th century) Muslim philosophers and poets, artists and scientists, princes and laborers created a unique culture that has influenced societies on every continent. Here documentary writer Howard Turner offers a fully illustrated, highly accessible introduction to the scientific achievements of medieval Islam. Howard Turner opens with a historical overview of the spread of Islamic civilization from the Arabian peninsula eastward to India and westward across northern... 

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