Lithium ion conduction

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-... 

Initial measurements carried out on PEO-alkali metal salt complexes indicated that the observed conductivities were mostly ionic with little contribution from electrons. It should be noted that the ideal electrolyte for lithium rechargeable batteries is a purely ionic conductor and, furthermore, should only conduct lithium ions. Contributions to the conductivity from electrons reduces the battery performance and causes self-discharge on storage. Salts with large bulky anions are used in order to reduce ion mobility, since contributions to the conductivity from anions produces a concentration gradient that adds an additional component to the resistance of the electrolyte. 

Recent studies also reveal that nanosized fillers are more effective in enhancing the ionic conductivity, lithium ion transference number and electrochemical stability (Kumar et al., 1994). Wang et al. (2010) introduced a fast ionic conductor with Lij jAlSO jTij 7(PO )j as filler in the PEO matrix. The authors achieved a high ionic conductivity of 4.53 x 10 S/cm at room temperature. 

Mixed-conducting lithium-ion-doped emeraldine polyaniline (PAni)-PEO blends have been developed in order to achieve optimal electronic-ionic conductivity balance in nano-tin composite anodes. They found that the SEI impedance of the composite anodes increases with a decrease in PEO content and is much lower in pressed than in cast electrodes. Nano-Sn, AlSi , and Li Sn powders were studied by EIS to determine the electrochemical kinetics and intrinsic resistance during initial lithium insertion-extraction. It was shown that the SEI formed on particle surfaces, together with particle pulverization are responsible for the high contact resistance. 

An organic polymer able to conduct lithium ions. The best-known example is polyethylene oxide. The polymer is, however, modified to lower the temperature where acceptable conductivity is obtained. The published literature suggests that about 373 K is the minimum temperature for such polymers to have the properties for a moderate current battery. The advantage of a polymer electrolyte lies in the possibility of a totally solid-state battery and, hence, great flexibility in the shape and packing of the battery as well as improved safety. 

All four polymorphs conduct lithium ions but the level of mobility in the different structures varies considerably. Some data from these polymorphs are collected in Figure 3.16. 

This discussion shows that the gel electrolyte must match the use of the battery, requiring optimization of the composition of the gel polymer electrolyte, the supporting salt and its concentration, and the solvent. PAN gel electrolytes made using different solvents, lithium salts, and composition will display different behaviors with respect to the ionic conductivity, lithium-ion transference number, electrochemical window, cyclic voltam-metric behavior, and compatibility with electrodes. Table 11.1 lists the ionic conductivity at room temperature of some gel electrolytes based on PAN. Because the PAN chain contains highly polar -CN groups, which exhibit poor compatibility with lithium metal electrodes, the passivation of the interface between the gel electrolyte and lithium metal electrode is crucial. At the same time, PAN has a high crystallization tendency. At elevated temperatures, the liquid electrolyte and plasticizer will separate therefore, the polymer is modified, mainly by copolymerization and cross-linking. 

While the result should not have very exact physical meaning, as an exercise, calculating the f potential of lithium ion, knowing that its equivalent conductivity is 39 cm /(eq)(ohm) in water at 25°C. 

Lithium Nitride. Lithium nitride [26134-62-3], Li N, is prepared from the strongly exothermic direct reaction of lithium and nitrogen. The reaction proceeds to completion even when the temperature is kept below the melting point of lithium metal. The lithium ion is extremely mobile in the hexagonal lattice resulting in one of the highest known soHd ionic conductivities. Lithium nitride in combination with other compounds is used as a catalyst for the conversion of hexagonal boron nitride to the cubic form. The properties of lithium nitride have been extensively reviewed (66). 

A second type of soHd ionic conductors based around polyether compounds such as poly(ethylene oxide) [25322-68-3] (PEO) has been discovered (24) and characterized. These materials foUow equations 23—31 as opposed to the electronically conducting polyacetylene [26571-64-2] and polyaniline type materials. The polyethers can complex and stabilize lithium ions in organic media. They also dissolve salts such as LiClO to produce conducting soHd solutions. The use of these materials in rechargeable lithium batteries has been proposed (25). 

Good results are obtained with oxide-coated valve metals as anode materials. These electrically conducting ceramic coatings of p-conducting spinel-ferrite (e.g., cobalt, nickel and lithium ferrites) have very low consumption rates. Lithium ferrite has proved particularly effective because it possesses excellent adhesion on titanium and niobium [26]. In addition, doping the perovskite structure with monovalent lithium ions provides good electrical conductivity for anodic reactions. Anodes produced in this way are distributed under the trade name Lida [27]. The consumption rate in seawater is given as 10 g A ar and in fresh water is... 

The deposition points on the lithium electrode are the points at which the protective film has a higher lithium-ion conductivity. One example of these deposition points are the pits on the lithium anode caused by discharge. Crystalline defects and the grain boundaries in lithium may also initiate deposition. 

According to this model, the SEI is made of ordered or disordered crystals that are thermodynamically stable with respect to lithium. The grain boundaries (parallel to the current lines) of these crystals make a significant contribution to the conduction of ions in the SEI [1, 2], It was suggested that the equivalent circuit for the SEI consists of three parallel RC circuits in series combination (Fig. 12). Later, Thevenin and Muller [29] suggested several modifications to the SEI model ... 

This section reports on the current state of knowledge on nonaqueous electrolytes for lithium batteries and lithium-ion batteries. The term electrolyte in the current text refers to an ion-conducting solution which consists of a solvent S and a salt, here generally a lithium salt. Often 1 1-salts of the LiX type are preferred for reasons given below only a few l 2-salts Li2X have attained some importance for batteries, and 1 3-salts Li3X are not in use. 

It is worth mentioning that single-ion conductivities of lithium ions and anions at infinite dilution, and transference numbers of ligand-solvated lithium ions estimated therefrom, increase due to the replacement of more than one (generally four) solvent molecules. Table 6 demonstrates this beneficial feature. 

Table 6. Single-ion conductivities of solvated lithium ions and anions at 25 °C in PC at infinite dilution [13]...

There is a difference in the behavior of benzenediolatoborate and naphthalenedio-latoborate solutions on the one hand, and lithium bis[2,2 -biphenyldiolato(2-)-0,0 ] borate (point 5 in fig. 8) lithium bis[ sali-cylato (2-) Jborate (point 6) or benzene-diolatoborate/phenolate mixed solutions on the other (Fig.8). This can be tentatively explained by the assumption of different decomposition mechanisms due to different structures, which entail the formation of soluble colored quinones from benzenediolatoborate anions and lithium-ion conducting films from solutions of the latter compounds (points 5 and 6) [80], The assumption of a different mechanism and the formation of a lithium-ion conducting, electronically insulating film is supported by... 

Figure 10 shows the voltage windows of chelatoborates. The question mark ( ) indicates the formation of lithium-ion conducting films, preventing the electrolyte from decomposition the numbers refer to the compounds mentioned in this section of the text. 

A 0.2 mol L"1 LiCl/THF solution possesses only very low conductivity of 1.6xl0"6 Scm"1. Addition of N(CH2 CH2NR2)3(R = CF3S02 short nomenclature M6R) yields an increase in conductivity by three orders of magnitude to 1.7 x 10 3 S cm"1. This approach is seemingly especially useful for battery electrolytes, because the transference number of the lithium ion is increased. Conceptually this approach is similar to the use of lith-... 

TablelO. Conductivities of various lithium ion containing liquid electrolytes...

Table 1. Conductivities, activation enthalpies, and other aspects of fast lithium-ion solid conductors...

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