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Improvement of life-time is an important issue in the development of Li-ion batteries. Aging mechanisms limiting the life-time can efficiently be characterized by physico-chemical analysis of aged cells with a variety of complementary methods. This study reviews the state-of-the-art literature on Post-Mortem analysis of Li-ion cells, including disassembly methodology as well as physicochemical characterization methods for battery materials. A detailed scheme for Post-Mortem analysis is deduced from literature, including pre-inspection, conditions and safe environment for disassembly of cells, as well as separation and post-processing of components. Special attention is paid to the characterization of aged materials including anodes, cathodes, separators, and electrolyte. More specifically, microscopy, chemical methods sensitive to electrode surfaces or to electrode bulk, and electrolyte analysis are reviewed in detail. The techniques are complemented by electrochemical measurements using reconstruction methods for electrodes built into half and full cells with reference electrode. The changes happening to the materials during aging as well as abilities of the reviewed analysis methods to observe them are critically discussed. Li-ion batteries are currently used in everyday objects such as smart-phones, power tools and tablet computers as well as in the growing fields of light electric vehicles (LEVs), unmanned aerial vehicles (UAVs), battery electric vehicles (BEVs), hybrid electric vehicles (HEVs), and plug-in hybrid electric vehicles (PHEVs). [1][2][3][4] Furthermore, the rise of renewable energy sources like wind and solar power, which are only intermittently available, demands reliable and highly flexible stationary energy storage solutions, which provide high capacities and predictable life-times. 2,5Aging of Li-ion batteries is a general problem for manufacturers as they have to guarantee long-term reliability of their products. For state-of-the-art cells, degradation effects on the material level lead to capacity fade and resistance increase on the cell level. The aging state of a battery is often characterized by the state-of-health (SOH) in % according to 3,16,22,[29][30][31] SO H(t) = discharge capacity (t) discharge capacity (t = 0)[1]where t represents the aging time. In general, one has to differentiate between cycling 7,16,18,21,[23][24][25]32 and calendar aging. 7,19,[21][22][23][24]27 Since commercial Li-ion cells can be subject to calendar aging in the time between manufacturing and delivery, it is good practice to measure the discharge capacity at t = 0 for each cell that undergoes an aging test. Since the discharge capacity depends mainly on temperature, depth-of-discharge (DOD), and discharge current, the SOH is usually monitored by regular check-ups with defined parameter sets, 7,16,21,23,24 which can vary depending on the application. Typically, a temperature of 25• C, 16,22,24 DOD of 100%, 16,21 and discharge rates of 1C 7,16,21,22,24 or lower 23 are used in check-ups. The performance dec...

Deposition of metallic Li is a severe aging mechanism in Lithium-ion cells. This study evaluates the influence of the main operating parameters leading to deposition of Li: temperature, charging C-rate, and end-of-charge voltage. Therefore both, graphite anodes and NMC cathodes from commercial 16Ah pouch cells are reconstructed into 3-electrode full cells Due to their comparably high energy and power densities, Lithiumion batteries are currently used in state-of-the-art electric cars.1-3 In automotive applications, battery life-times of 10 years are expected for customer acceptance. However, it is known that life-time of Lithiumion batteries is limited by aging mechanisms.4-11 One of these aging mechanisms is deposition of metallic Li on anodes. 8,[12][13][14][15] Due to the high chemical reactivity of metallic Li, it readily reacts with electrolyte leading to capacity loss of the cell. 8,9,14,16 It is known that Li deposition mainly depends on (i) charging C-rate, 14,16,17 (ii) temperature, 8,9,12,14,[16][17][18] and (iii) end-of-charge voltage/state-of-charge.14,17 Several authors reported trends for variation of only one of these parameters respectively. E.g. low temperatures during charging are reported to lead to Li plating on graphite anodes. 8,9,14,16,19 However, there is a dearth of experimental results on the topic how specific combinations of operating conditions affect Li deposition. Since such experiments are highly interesting for extension of cycle life 14,20 and improvement of cell safety, 21 this is the topic of the present paper.The reason for deposition of Li on anodes are negative anode potentials E anode vs. (Li/Li + ). 8,12,14,20 Unfortunately, in commercial cells only the cell voltageand not the anode potential vs. (Li/Li + ) can be measured. The reason is that commercial cells do not contain a third reference electrode.Measurements of E anode in full cells would allow detection of Li deposition on anodes (condition: E anode vs. (Li/Li + ) < 0 V). Indeed, by introducing an additional reference electrode, such as metallic Li, the electrode potentials are accessible. 8,12,14,20,22,23 We note that such measurements are also not possible in a halfcell configuration with e.g. either only a graphite anode vs. a Li counter electrode or only a NMC cathode vs. a Li counter electrode, since the interaction between anode and cathode is not taken into account. Instead, 3-electrode full cells with the following electrodes are required to detect Li deposition correctly: (i) anode (e.g. graphite), (ii) cathode (e.g. NMC), and (iii) reference electrode (e.g. metallic Li).Furthermore, it is well-known that the reference electrode has to be positioned near the anode in order to minimize the Ohmic drop and to measure its potential accurately. 24 For example, in aqueous z E-mail: thomas.waldmann@zsw-bw.de systems, this is achieved by a Luggin-Haber capillary. 24 Simulations by Dees et al. also showed that the best position for a reference electrode in Lithium-ion cells is between anode and cathode. 25 The same...