Lithium intercalation, graphite

Holzwarth, N. A. W., S. G. Louie, and S. Rabii. 1983. Lithium-intercalated graphite Self-consistent electronic structure for stages one, two, and three. Phys. Rev. B 28 1013-1025. 

Samuelson, L. and I. P. Batra. 1980. Electronic properties of various stages of lithium intercalated graphite. J. Phys. C 13 5105-5124. 

Richard M. N., Dahn J. R. Accelerating Rate Calorimetry Study on the Xhermal Stability of Lithium Intercalated Graphite in Electrolyte. I. Experimental, J. Electrochem. Soc. 1999, 146, 2068-2077. 

Richard MN, Dahn JR (1999) Accelerating rate calorimetry study on the thermal stability of lithium intercalated graphite in electrolyte. Modeling the results and predicting differential scanning calorimeter curves. J Electrochem Soc 146(6) 2078-2084... 

Rasch, B. Cattaneo, E. Novak, P. Vielstich, W. (1991). The influence of water on the oxidation of propylene carbonate on platinum. An electrochemical, in-situ FTIR and on-line MS study. Electrochimica Acta, 36, 9, (1991), 1397-1402 Richard, M. N. Dahn, J. R. (1999). Accelerating rate calorimetry study on the thermal stability of lithium intercalated graphite in electrolyte. I. Experimental. Journal of the Electrochemical Society, 146, 6, (1999), 2068-2077... 

Figure 2.11 Gravimetric capacity of bulk, nanociystalline, and amorphous films of silicon and germanium over 50 cycles. The dotted line represents the theoretical capacity for the commercially available lithium-intercalated graphite.

Because of the variety of available carbons, a classification is inevitable. Most carbonaceous materials which are capable of reversible lithium intercalation can be classified roughly as graphitic and non-graphitic (disordered). 

Intercalation compounds of lithium and other species into the layered structure of graphite, synthesized by chemical methods, have been known for a long time. In the mid-1980s, the possibility of a reversible lithium intercalation from apro-tic solutions containing lithium salts into certain carbonaceous materials was discovered ... 

The intercalation compounds of lithium with graphite are very different in their behavior from intercalation compounds with oxides or halcogenides. Intercalation processes in the former compounds occur in the potential region from 0 to 0.4 V vs. the potential of the lithium electrode. Thus, the thermodynamic activity of lithium in these compounds is close to that for metallic lithium. For this reason, lithium intercalation compounds of graphite can be used as negative electrodes in batteries rather than the difficultly of handling metallic lithium, which is difficult to handle. 

Figure 4. Depiction of lithium intercalated into the carbon/graphite lattice.

Figure 17. The basal plane and prismatic surfaces of graphite have different functions with respect to lithium intercalation and de-intercalation (= charge, discharge, self-discharge, etc.). As a consequence, only the electrolyte decomposition product layers at the prismatic surfaces have SEIfunction. Any processes related with electrolyte decomposition product layers at the basal plane surfaces (= non-SEI layers) therefore can not be directly related to electrochemical data such as charge, discharge, self-discharge, etc. The situation is even more complex as the SEI composition and morphology at the basal and prismatic surface...

Due to its high energy density (3,860 mAh/g) and low voltage, lithium is the most attractive metal of the periodic table for battery application. Unfortunately lithium metal, and most of its alloys cannot be used in rechargeable batteries because of their poor cyclability. Therefore, lithium intercalation compounds and reversible alloys are among today s materials of choice for subject application. The most common active materials for the negative electrodes in lithium-ion battery applications are carbonaceous materials. The ability of graphitized carbonaceous materials to... 

Naji A., Willmann P., and Billaud D. Electrochemical Intercalation of Lithium into Graphite Influence of the Solvent Composition and the Nature of the Lithium Salt. Carbon, 36, 1347-1352 (1998). 

Billaud D., Henry F.X. and Willmann P. Electrochemical Synthesis of Binary Graphite-Lithium Intercalation Compounds. Mat. Res. Bull., 28, 477-483 (1993). 

Figure 6. The entropy of lithium intercalation into natural graphite, after [22],...

The source carbon materials show a significant electrochemical activity for lithium intercalation though the reversible capacity is relatively low and tends to reduce with cycling. For the thermally expanded graphite... 

Abe, T., Kawabata, N., Mizutani, Y., Inaba, M., and Ogumi, Z., Correlation between cointercalation of solvents and electrochemical intercalation of lithium into graphite in propylene carbonate solution, J. Electrochem. Soc. (2003) 150 (3), A257-A261. 

Guerard D., Herold A. Intercalation of lithium into graphite and other carbons. Carbon 1975 13 337-45. 

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