(Keynote) 25th Anniversary of Lithium Ion Batteries: Carbonaceous Anodes֠ and More ?

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Carbons are used in electrochemical energy storage and conversion devices, such as super-capacitors, fuel cells and hydrogen storage devices as well as batteries. Here carbon is acting in multiple functions, e.g., as negative or positive electrode material, as conductive agent, as catalyst carrier, as current collector (CC) or as “primer” for CCs, or as porous electrolyte- and gas-penetrated electrode (review [1]). Since its beginnings [2, 3], lithium ion batteries (LIBs) use carbons as lithium ion insertion/intercalation hosts at the anode. The intercalation chemistry of Li in graphite is known from the mid 1950ies [4]. Apart from the low and relatively constant de-insertion/de-intercalation potential, the high electronic and ionic conductivity at room temperature, low costs, and the appreciable Li storage capacity, one major advantage of carbonaceous anodes is there unique reactivity with typical LIB electrolytes, leading to an effective solid electrolyte interphase (SEI), which – after the SEI discovery on metallic Li [1, 5, 6] - may be considered as the “2ndwonder” in alkali battery development [1,7,8]. The beneficial combination of graphitic anodes with additive-stabilized organic carbonate solvent based electrolytes is still the benchmark. It is common wisdom, that anode and electrolyte development go hand in hand and that it took 20 years to find the “right” electrolyte for graphitic anodes. The present struggle for electrolytes compatible with high voltage cathodes [9] may give us an indication of the hurdles that were overcome at that time. While Li storage metals such as Sn and Si show high promise as high capacity anode materials, the SEI formation process is not limited to the first few cycles as for graphite. This is not only related to the large volume expansion/contraction of the lithium storage metals, leading to a very dynamic surface and interface with the electrolyte [10], but also due to the different reactivity of graphite and metallic hosts vs. the electrolyte [11]. In fact, LIB with lithium storage metal anodes “die” anode failure affects the cathode performance [12]; another proof for the necessity of a systemic approach to materials research. Other insertion anodes such as Li4Ti5O12[13] or the numerous materials that function according to a so-called conversion mechanism [14] are a visible proof for the enormous capability of our community to find new and exotic electrode materials, which in several cases show surprising reaction mechanisms. Practical relevance is however not always in the focus of these inventions. With Si anodes as the “hope for next generation anodes” since >10 years, the future of commercial anodes seems to be on a clear path. Whether other high capacity anodes will make a practical impact is very uncertain. Apart from Si, the rechargeable metallic Li electrode is a more probable guess currently. References (History of LIB anodes has been influenced by many research groups. The following literature can be only selective) M. Winter; K.-C. Moeller; J. O. Besenhard: Carbonaceous and graphitic anodes: basic aspects, -in: G. A. Nazri; G. Pistoia (Eds.): Lithium Batteries: Science and Technology, New York: Kluwer Academic Publishers, 2004, 144-194.T. Nagaura, in Progress in Batteries and Solar Cells Vol. 10 (Eds: JEC Press Inc. and IBA Inc.), JEC Press Inc., Brunswick OH 1991, p. 218.T. Nagaura, K. Tozawa, in Progress in Batteries and Solar Cells Vol. 9 (Eds.: JEC Press Inc. and IBA Inc.), JEC Press Inc., Brunswick, OH, 1990, p. 209.A. Hérold, Bull. Soc. Chim. France 1955, 187, 999.A. N. Dey, Electrochem. Soc. Fall Meeting, 1970, Abstr. 62.E. Peled, J. Electrochem. Soc., 1979, 126, 40.R. Fong, U. von Sacken, J. R. Dahn, J. Electrochem. Soc., 1990, 137, 2009.M. Winter, Zeitschrift fuer Physikalische Chemie, 2009, 223, 1395.J. Kasnatscheew; M. Evertz; B. Streipert; R. Wagner; R. Klöpsch; B. Vortmann; H. Hahn; S. Nowak; M. Amereller; A-C Gentschev; P. Lamp; M. Winter; Phys. Chem. Chem. Phys., 2016, 18, 3956.M. Winter; W. K. Appel; B. Evers; T. Hodal; K.-C. Möller; I. Schneider; M. Wachtler; M. R. Wagner; G. H. Wrodnigg; J. O. Besenhard, Chem. Monthly, 2001, 132, 473.M. R. Wagner; P. Raimann; K.-C. Möller; J. O. Besenhard; M. Winter, Electrochem. Solid St. Lett., 2004, 7, A201.S. Krüger; R. Klöpsch; J. Li; S. Nowak; S. Passerini; M. Winter; J. Electrochem. Soc.., 2013, 160 (4), A542.D.W. Murphy, R.J. Cava, S.M. Zahurak, A. Santoro, Solid State Ionics, 9–10 (1983), 413.P. Poizot, S. Laruelle, S. Grugeon, L. Dupont & J-M. Tarascon, Nature, 2000, 407, 496.