Lithium passivation layer

This is only possible because lithium forms a passive layer in solutions containing higher amounts of caustic [17, 18]. 

It is now well established that in lithium batteries (including lithium-ion batteries) containing either liquid or polymer electrolytes, the anode is always covered by a passivating layer called the SEI. However, the chemical and electrochemical formation reactions and properties of this layer are as yet not well understood. In this section we discuss the electrode surface and SEI characterizations, film formation reactions (chemical and electrochemical), and other phenomena taking place at the lithium or lithium-alloy anode, and at the Li. C6 anode/electrolyte interface in both liquid and polymer-electrolyte batteries. We focus on the lithium anode but the theoretical considerations are common to all alkali-metal anodes. We address also the initial electrochemical formation steps of the SEI, the role of the solvated-electron rate constant in the selection of SEI-building materials (precursors), and the correlation between SEI properties and battery quality and performance. 

According to the depth profile of lithium passivated in LiAsF6 / dimethoxyethane (DME), the SEI has a bilayer structure containing lithium methoxide, LiOH, Li20, and LiF [21]. The oxide-hydroxide layer is close to the lithium surface and there are solvent-reduction species in the outer part of the film. The thickness of the surface film formed on lithium freshly immersed in LiAsF /DME solutions is of the order of 100 A. 

It was concluded [93, 94J that, on long cycling of the lithium-ion battery, the passivating layer on the carbon anode becomes thicker and more resistive, and is responsible, in part, for capacity loss. 

Upon an increase of the anodic reverse potential finally up to 8 V versus Li the cyclic voltammogran corresponding to Fig. 9 remains unchanged, showing that the passivating layer at the electrode also protects the solvents (PC and DME) from being oxidized. Subsequent deposition and dissolution of lithium at the passivated electrodes remains possible when the electrode is passivated but the cycling efficiency decreases. 

The HRTEM observation of the cross section of a coated fiber showed that the core is constituted of aromatic layers highly misoriented, whereas they are preferentially oriented in parallel for the thin coating pairs of stacked layers form mainly Basic Structural Units (BSUs) in which the average interlayer distance is smaller than between the aromatic layers in the bulk of the fiber. Since the nanotexture is more dense for the pyrolytic carbon than for the fiber itself, it acts as a barrier which prevents the diffusion of the large solvated lithium ions to the core of the fiber, allowing the passivation layer to be less developed after this treatment. Hence, the major amount of lithium inserted is involved in the reversible contribution therefore this composite material is extremely interesting for the in-situ 7Li NMR study of the reversible insertion. 

Figure 5. 7Li NMR spectra recorded during 3 cycles of reversible lithium insertion-deinsertion in the composite carbon electrode. The peak at 0ppm is due to ionic lithium (Li+PF6 and passivation layer). The peak of lithium at 263 ppm is not shown.

The properties of lithium metal were described in Chapter 4, where particular note was made of its high specific capacity and electrode potential. However, because of its highly electropositive nature, it is thermodynamically unstable in contact with a wide variety of reducible materials. In particular, lithium reacts with components of most electrolytes to form a passivating layer. Film formation of this type ensures long shelf life for primary lithium cells, but causes severe problems when the electrode is cycled in a secondary cell. 

Work has therefore been devoted by a number of developers to improving the cyclability of the lithium metal electrode. Since passivation of lithium is an unavoidable phenomenon, one approach has been directed to the promotion of uniform and smooth surface passivation layers, for example by selecting the most appropriate combination of solvents and electrolyte salts. An example is the inclusion of 2-methyltetrahydrofuran (2-Me-THF), since the presence of the methyl group slows down the reactivity towards the lithium metal. The selection of fluorine-based elec-... 

The potential window is one of the most important physical properties for the selection of a solvent for electrolysis. However, it should also be noted that the surface layer on the electrode, which is formed by chemical or electrochemical deposition, often stabilizes the system. For example, Katayama reported that a lithium ion conductive passivated layer, which is formed on the tungsten electrode as a result of reductive decomposition of the cation of the IL during the first sweeps, enables the reversible deposition and dissociation of Li metal [104], Howlett et al. have also discussed this extensively [112a-c]. 

As already mentioned, salt-containing liquid solvents are typically used as electrolytes. The most prominent example is LiPF6 as a conductive salt, dissolved in a 1 1 mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) as 1 molar solution. It should be mentioned that this electrolyte is not thermodynamically stable in contact with lithium or, for example, LiC6. Its success comes from the fact that it forms an extremely stable passivation layer on top of the electrode, the so-called solid-electrolyte interface (SEI) [35], Key properties of such SEI layers are high Li+ and very low e conductivity - that is, they act as additional electrolyte films, where the electrode potential drops to a level the liquid electrolyte can withstand [36],... 

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