Lithium insertion

Lithium insertion in microporous hard carbons (region 3 in Fig. 2) is described in section 6. High capacity hard carbons can be made from many precursors, such as coal, wood, sugar, and different types of resins. Hard carbons made from resole and novolac resins at temperatures near 1000°C have a reversible capacity of about 550 mAh/g, show little hyteresis and have a large low voltage plateau on both discharge and charge. The analysis of powder X-ray diffraction. 

There are many ways to eharaeterize the strueture and properties of carbonaceous materials. Among these methods, powder X-ray diffraetion, small angle X-ray scattering, the BET surfaee area measurement, and the CHN test are most useful and are deseribed briefly here. To study lithium insertion in carbonaeeous materials, the eleetroehemieal lithium/earbon eoin eell is the most eonvenient test vehicle. 

Fig. 23. When lithium inserts in hydrogen-containing carbon, some lithium atoms bind on the hydrogen-terminated edges of hexagonal carbon fragments. This causes a change from sp to sp bonding [37].

Additional samples were prepared from the three resins and were heated at temperatures between 940° and 1100°, under different inert gas flow rate and with different heating rates. The samples have different microporosities and show different capacities for lithium insertion. The results for all the carbons prepared from resins are shown in Fig. 32, which shows the reversible capacity plotted as a function of R. The reversible capacity for Li insertion increases as R decreases. This result is consistent with the result reported in reference 12,... 

A lithium cluster in the micropores of the carbon sample has a very similar environment as lithium atoms in metallic lithium. Hence, we observe long low-voltage plateaus on both discharge and charge for lithium insertion in the microporous carbon. 

This review focuses on the structural stability of transition metal oxides to lithium insertion/extraction rather than on their electrochemical performance. The reader should refer to cited publications to access relevant electrochemical data. Because of the vast number of papers on lithium metal oxides that have been published since the 1970s, only a selected list of references has been provided. 

Electrodes that are prepared from acid-leached LT-LiCo, xNix02 compounds (0< x<0.2) show significantly enhanced electrochemical behavior over the parent LT-LiCo1 xNix02 structure. The improved performance has been attributed to the formation of compounds with a composition and cation arrangement close to the ideal Li[B2]04 spinel structure (B = Co, Ni) [62]. These spinel-type structures have cubic symmetry, which is maintained on lithiation the unit cells expand and contract by only 0.2 percent during lithium insertion and extraction. 

Beginning in the early 1980s [20, 21] metallic lithium was replaced by lithium insertion materials having a lower standard redox potential than the positive insertion electrode this resulted in a "Li-ion" or "rocking-chair" cell with both negative and positive electrodes capable of reversible lithium insertion (see recommended papers and review papers [7, 10, 22-28]). Various insertion materials have been proposed for the anode of rechargeable lithium batteries,... 

From a thermodynamic point of view, apart from charge density and specific charge, the redox potential of lithium insertion into/removal from the electrode materials has to be considered also. For instance, the redox potential of many Li alloys is between -0.3 and -1.0 V vs. Li/Li+, whereas it is only -0.1 V vs. 

Figure 2. Redox potentials for lithium insertion into/removal from several anode materials for lithium cells.

Recently lithium insertion in quaternary thiospinels like (Cug.giGeDg.ggjga [Fe4Sni2]i6dS32 and (Cu4.xGen3o+x)8a[Co4Sni2]i6dS32 have been reported [15, 16]. It is believed that the vacancies in the tetrahedral 8 a sites result from a topotac-tic substitution of four Cu ions by one Ge ion. 

Fig. 6.4 Layered structure of LixTiSa, showing the lithium ions between the TiSa sheets. This is an anion close-packed lattice in which alternate layers between the anion sheets are occupied by a redox-active titanium atom. Lithium inserts itself into the empty remaining layers. (Adapted from [68])...

Suitable polymer anodes have not been found instead, in the search for improved lithium hosts, lithium-inserting carbon materials have been developed and batteries produced, usually with a metal oxide or sulfide anode (hence they are not considered fnrther here). 

Boron-containing carbons synthesized by co-pyrolysis of coal-tar pitch with pyridine-borane complex (series 25Bn) have already been considered as hosts for lithium insertion [4], Unlike the commercial graphites described above, the boron-doped carbon 25B2 (WUT) as received was not suitable for direct use in the cylindrical cell due to very large and hard particles. This feature makes the coating process very difficult. 

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