Materials lithiated

Starting Materials Lithiation Conditions R2I Conditions Ratio EjZ Yield (%) Ref... 

Thermodynamic enolates are generated at room temperature or reflux by conducting the deprotonation in the presence of a small amount of a weak acid (usually a 1-2% excess of the ketone starting material). Lithiated bases ai e preferred for thermodynamic enolate generation because lithium enolates have a fairly covalent oxygen-lithium bond. Consequently, the most stable enolates will be those that have the most highly substituted double bond. 

Figure 1. Specific charges and charge densities of several lithiated anode materials for lithium batteries, calculated by using data from Refs, [10, 32-35], Li4 denotes a fourfold excess of lithium, which is necessary to attain a sufficient cycle life.

During electrochemical reduction (charge) of the carbon host, lithium cations from the electrolyte penetrate into the carbon and form a lithiated carbon Li rCn. The corresponding negative charges are accepted by the carbon host lattice. As for any other electrochemical insertion process, the prerequisite for the formation of lithiated carbons is a host material that exhibits mixed (electronic and ionic) conductance. 

The electrochemical performance of lithiated carbons depends basically on the electrolyte, the parent carbonaceous material, and the interaction between the two (see also Chapter III, Sec.6). As far as the lithium intercalation process is concerned, interactions with the electrolyte, which limit the suitability of an electrolyte system, will be discussed in Secs. 5.2.2.3,... 

Apart from manifold structures, carbons can have various shapes, forms, and textures, including powders with different particle size distributions, foams, whiskers, foils, felts, papers, fibers [76, 77], spherical particles [76] such as mesocarbon microbeads (MCMB s) [78], etc. Comprehensive overviews are given, for example in [67, 71, 72], Further information on the synthesis and structures of carbonaceous materials can be found in [67, 70, 72, 75, 79]. Details of the surface composition and surface chemistry of carbons are reviewed in Chapter II, Sec. 8, and in Chapter III, Sec. 6, of this handbook. Some aspects of surface chemistry of lithiated carbons will also be discussed in Sec. 5.2.2.3. 

Figure 19. The volumes of several anode materials tor lithium ion cells before (gray) and after (black) lithiation.

Kinetic stability of lithium and the lithiated carbons results from film formation which yields protective layers on lithium or on the surfaces of carbonaceous materials, able to conduct lithium ions and to prevent the electrolyte from continuously being reduced film formation at the Li/PC interphase by the reductive decomposition of PC or EC/DMC yielding alkyl-carbonates passivates lithium, in contrast to the situation with DEC where lithium is dissolved to form lithium ethylcarbonate [149]. EMC is superior to DMC as a single solvent, due to better surface film properties at the carbon electrode [151]. However, the quality of films can be increased further by using the mixed solvent EMC/EC, in contrast to the recently proposed solvent methyl propyl carbonate (MPC) which may be used as a single sol-... 

Previous syntheses of terminal alkynes from aldehydes employed Wittig methodology with phosphonium ylides and phosphonates. 6 7 The DuPont procedure circumvents the use of phosphorus compounds by using lithiated dichloromethane as the source of the terminal carbon. The intermediate lithioalkyne 4 can be quenched with water to provide the terminal alkyne or with various electrophiles, as in the present case, to yield propargylic alcohols, alkynylsilanes, or internal alkynes. Enantioenriched terminal alkynylcarbinols can also be prepared from allylic alcohols by Sharpless epoxidation and subsequent basic elimination of the derived chloro- or bromomethyl epoxide (eq 5). A related method entails Sharpless asymmetric dihydroxylation of an allylic chloride and base treatment of the acetonide derivative.8 In these approaches the product and starting material contain the same number of carbons. 

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