A New Method for Quantitative Marking of Deposited Lithium by Chemical Treatment on Graphite Anodes in Lithium‐Ion Cells

Krämer, Yvonne; Birkenmaier, Claudia; Feinauer, Julian; Hintennach, Andreas; Bender, Conrad L.; Meiler, M.; Schmidt, Volker; Dinnebiér, Robert E.; Schleid, Thomas

doi:10.1002/chem.201406606

Cited by 21 publications

(23 citation statements)

References 25 publications

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“…16 After conservation of Li deposition by chemical reaction of its surface with isopropanol, powder X-ray diffraction (PXRD) was used to identify Li 2 CO 3 . 150 The results were in agreement with EDX and FTIR measurements. 150 XRD is a common method to conclude on lattice constants of crystalline active materials.…”

Section: -211supporting

confidence: 84%

Review—Post-Mortem Analysis of Aged Lithium-Ion Batteries: Disassembly Methodology and Physico-Chemical Analysis Techniques

Waldmann

Iturrondobeitia

Kasper

et al. 2016

J. Electrochem. Soc.

230

149

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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...

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Section: -211supporting

confidence: 84%

Review—Post-Mortem Analysis of Aged Lithium-Ion Batteries: Disassembly Methodology and Physico-Chemical Analysis Techniques

Waldmann

Iturrondobeitia

Kasper

et al. 2016

J. Electrochem. Soc.

230

149

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“…Assuming, that the lithium phase can not be fully depleted, a Butler-Volmer-like expression can be used for the exchange-current density: (18) Since lithium metal has a higher conductivity than graphite, we can approximate the electrical potential Φ Pl in the plated lithium by the electrical potential in the graphite Φ So . Hence the plating condition can equivalently be expressed by the intercalation overpotential η intercalation and the open circuit potential U 0 (c So )…”

Section: Lithium Platingmentioning

confidence: 99%

“…Inhomogeneities on electrode scale can theoretically enter in the form of spatially dependent morphological parameter, but are usually neglected. Modifi- 35 cations like this might be important to investigate experimentally observed non-uniform plated lithium distribution in large pouch cells [18]. The role of the always present local fluctuation of the electrochemical environment due to the underlying particle structure of the electrode cannot be resolved within this approach.…”

Section: Introductionmentioning

confidence: 99%

Influence of local lithium metal deposition in 3D microstructures on local and global behavior of Lithium-ion batteries

Hein

Latz

2016

Electrochimica Acta

112

119

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On of the major degradation processes in lithium ion batteries is the deposition of metallic lithium on the surface of the active particles in the negative electrode. In this paper we present a fully 3D microstructure resolved simulation of the influence of plated lithium on the cell potential during discharge depending on the amount and position of plated lithium. Our simulations give insight on the most probable position of the first occurrence of plating within the electrode depending on applied current and ambient temperatures as well as on the subtle local electric current distributions during stripping of plated lithium upon discharge. Specifically a stripping induced intercalation of lithium ions in the supporting graphite material during discharge is discovered. This phenomenon, easily accessible to microstructure resolved simulations, leads to a violation of the relation between transferred charge during stripping and the amount of plated lithium. As a consequence the amount of plated lithium cannot be uniquely determined from the applied current and the length of the potential plateau during stripping. We show that the value and length of the plateau depends on the amount of plated lithium, the fraction of the surface area covered by lithium and the applied current.

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“…Lithium plating usually occurs during operation of the battery at low temperatures or high charging currents. Detection of this phenomenon is not straightforward, and often only indirect proof is given through the aging behavior, , the discharge cell voltage, or post-mortem analysis . A direct detection of lithium plating requires complex experimental setups, that is, electrochemical cells with optical windows, − or expensive instruments, that is, nuclear magnetic resonance instruments. − These approaches provide a mechanistic understanding; however, they are not feasible in practical applications.…”

Section: Introductionmentioning

confidence: 99%

An Electrochemical Model of Lithium Plating and Stripping in Lithium Ion Batteries

Hein

Danner

Latz

2020

ACS Appl. Energy Mater.

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The deposition of a metallic lithium phase on the surface of graphite anodes in lithium ion batteries is a major degradation process and causes inherent safety risks. Despite its importance for battery applications the detection of this so-called lithium plating process during battery charge is very challenging. Therefore, a mechanistic understanding of the Li plating mechanism and the identification of characteristic features in the charge curve of the battery are extremely important. We present an electrochemical model, which enables the description of the deposition and dissolution of a metallic lithium phase in three-dimensional microstructure resolved simulations of lithium ion batteries. The features of this model are demonstrated by simulating the overcharge of a graphite electrode in a half-cell configuration. Simulation results show the typical features of the “stripping-plateau”, which is often observed during discharge after Li plating occurrs. Moreover, a similar feature is observed at the onset of Li plating, which can serve as an indicator for lithium plating in lithium ion batteries during charging, for example, of electric vehicles. Finally, we investigate the impact of an inhomogeneous solid-electrolyte-interphase on the distribution of plated lithium, which highlights the effect of local structural heterogeneities on degradation phenomena.

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A New Method for Quantitative Marking of Deposited Lithium by Chemical Treatment on Graphite Anodes in Lithium‐Ion Cells

Cited by 21 publications

References 25 publications

Review—Post-Mortem Analysis of Aged Lithium-Ion Batteries: Disassembly Methodology and Physico-Chemical Analysis Techniques

Review—Post-Mortem Analysis of Aged Lithium-Ion Batteries: Disassembly Methodology and Physico-Chemical Analysis Techniques

Influence of local lithium metal deposition in 3D microstructures on local and global behavior of Lithium-ion batteries

An Electrochemical Model of Lithium Plating and Stripping in Lithium Ion Batteries

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