In Situ Detection of Lithium Plating on Graphite Electrodes by Electrochemical Calorimetry

Downie, Laura E.; Krause, L. J.; Burns, James T.; Jensen, L. D.; Chevrier, Vincent; Dahn, J. R.

doi:10.1149/2.049304jes

Cited by 132 publications

(101 citation statements)

References 23 publications

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“…In literature, such behavior was also observed for cells with Li plating. 21,43 At the beginning of cycling, the CEs drop by ∼1% and then increase again (see inset of Figure 2c). This indicates a decrease in side reactions after the first 5 cycles.…”

Section: Resultsmentioning

confidence: 92%

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Electrochemical, Post-Mortem, and ARC Analysis of Li-Ion Cell Safety in Second-Life Applications

Waldmann

Quinn

Richter

et al. 2017

J. Electrochem. Soc.

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Li-ion cells are used in a variety of mobile and stationary applications. Their use must be safe under all conditions, even for aged cells in second-life applications. In the present study, different aging mechanisms are taken into account for accelerating rate calorimetry (ARC) tests. 18650-type cells are cycled at 0 • C (Li plating expected) and at 45 • C (SEI growth expected). After extensive evaluation of the electrochemical results (voltage curve analysis, capacity fade, energy fade, Coulombic efficiency), the cells are tested by PostMortem analysis (CT, GD-OES, SEM) to reveal the main aging mechanisms and by ARC to test the safety behavior. Besides typical ARC results such as onset-of-self-heating, onset-of-thermal runaway and maximum temperatures, as well as acoustic responses of thermal runaway are evaluated and a method is developed to compare fresh cells and cells aged until different SOHs. It turns out that the safety of aged cells is not simply a function of the SOH. However, safety is strongly affected by the main aging mechanism and to the history of operating parameters during the life-time of the cell. Driven by the demand for higher capacity, lower volume, and lower weight, Li-ion technology was developed in the 1980s.1,2 Nowadays, Li-ion technology is used for energy storage in a large variety of applications, e.g. smartphones, tablets, or drones. In particular, electric vehicles in combination with renewable energy sources are promising for reducing climate change and the corresponding glacier melting and sea level rise which is influenced by burning fossil fuels.3-6 For all applications, the safety behavior under all specified operating conditions is most important.7-9 The same is true for aged Li-ion cells used in second-life applications, for example cells which are utilized in stationary energy storage applications after their usage in electric cars.In the past, failure of Li-ion cells led to product recalls which are very expensive for the manufacturers and unsettle customers, even if such incidents happen only in very few cases (ppm range).10 At the moment, safety tests have to be performed with Li-ion prototypes cells before market release. In these tests, fresh cells are always used, however, aged cells are usually neglected. Even if fresh cells show an acceptable safety behavior, this can change for aged cells. 7,[11][12][13][14][15] While some authors observed decreases for certain safety properties, 7,11,12 others found improvements. 12,13,15 It is well known that aging mechanisms change the properties of the materials inside Li-ion cells. [16][17][18][19] Operating conditions and materials have a strong influence on these aging mechanisms. 12,[20][21][22][23] We recently reported on a change of the aging mechanism with temperature for cycling aging of commercial 18650-type cells with graphite anodes and NMC/LMO cathodes. 20 This mechanism change is expressed by a V-shape in Arrhenius plots of the capacity fade rates obtained from cycling at different ambient temperatures. 20 This c...

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Section: Resultsmentioning

confidence: 92%

“…Significantly lower CE values indicate side reactions connected to irreversible capacity loss as shown by high precision measurements by Dahn's group. 21,[43][44][45] For the measurements at 25…”

Section: Resultsmentioning

confidence: 99%

Electrochemical, Post-Mortem, and ARC Analysis of Li-Ion Cell Safety in Second-Life Applications

Waldmann

Quinn

Richter

et al. 2017

J. Electrochem. Soc.

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“…Studies have been conducted to detect the onset of lithium plating, to measure the plating efficiency and also to see how changes to the cell chemistries impact lithium plating. [1][2][3][4][5] One of the clearest ways to detect the presence of lithium plating uses three electrode cells to measure the potential of the negative electrode and measure the state of charge at which it drops below 0 V vs Li/Li + , 1,2 however this cannot be done in commercial cells without a reference electrode.…”

mentioning

confidence: 99%

In-Situ Detection of Lithium Plating Using High Precision Coulometry

Burns

Stevens

Dahn

2015

J. Electrochem. Soc.

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281

229

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Plating of metallic lithium on the negative electrode in lithium-ion batteries can dramatically reduce cell lifetime, impact cell safety and must be avoided during normal cell operation. Due to the low efficiency of the lithium plating/stripping process relative to the intercalation/deintercalation of lithium from graphite, small amounts of lithium plating can be detected through high accuracy measurements of coulombic efficiency. In this study, coulombic efficiency versus charging rate was measured at different temperatures and for two cell types. Small changes to the coulombic efficiency during cycling resulting from small amounts of lithium plating during the charging process were detected using a high precision charger. Cells were disassembled and examined to confirm the presence of lithium plating at the rates predicted to cause plating. This work shows how high precision coulometry can be used to maximize the performance of the cell through battery management by varying the maximum charge rate as a function of temperature to avoid lithium plating. Lithium-ion batteries are currently used for portable electronics applications (cell phones, laptops, tablets, etc.) because their specific energy and lifetime are adequate for such devices. However, the use of Li-ion batteries for electrified vehicle battery packs requires much longer cycle and calendar life. In addition to the increased demands for longer battery lifetimes, new applications constantly strive to increase energy density and lower recharge time. However, due to the potential risk for deposition of metallic lithium on the negative electrode at high rates, recharge rates are typically limited by battery management electronics. Studies have been conducted to detect the onset of lithium plating, to measure the plating efficiency and also to see how changes to the cell chemistries impact lithium plating.1-5 One of the clearest ways to detect the presence of lithium plating uses three electrode cells to measure the potential of the negative electrode and measure the state of charge at which it drops below 0 V vs Li/Li + , 1,2 however this cannot be done in commercial cells without a reference electrode.Petzl and Danzer 3 show that the differential voltage and capacity discharge curves can be used to detect when lithium plating has occurred during a previous high rate charge. When lithium plating has occurred there is a feature in the voltage curve related to the stripping of lithium from the negative electrode due to the difference in potential between stripping of lithium and deintercalating lithium from the negative electrode. Large amounts of lithium plating need to have occurred in order for this feature in the differential capacity or voltage curve to be clearly distinguishable (Figure 3 in reference 3 shows the degree of lithium plating that has occurred for detection in the study). However, even small amounts of lithium plating during cycling of cells can shorten cell lifetime and impact safety and therefore greater sensitivity in detection of li...

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“…[3][4][5] In contrast, Li deposition and subsequent reaction with electrolyte is usually observed after charging at low temperatures and/or high rates. 4,[6][7][8][9][10][11] Li deposition causes rapid capacity decay 4,11 and can significantly reduce cell safety. 12 The reason for lithium deposition is anode polarization, which drops below 0 V vs. Li/Li + in the respective cases.…”

mentioning

confidence: 99%

“…Therefore, non-destructive methods for detection of Li deposition and quantification are under development by several groups. [7][8][9][10] In order to validate non-destructive detection methods, one has to be able to detect Li chemically after cell opening. Petzl et al recently used the reactivity of Li with water as a sign of metallic Li on graphite anodes.…”

mentioning

confidence: 99%

Detection of Li Deposition by Glow Discharge Optical Emission Spectroscopy in Post-Mortem Analysis

Ghanbari

Waldmann

Kasper

et al. 2015

ECS Electrochemistry Letters

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Glow discharge optical emission spectroscopy (GD-OES) is employed to detect and quantify Li deposition as a function of depth on graphite electrodes. Commercial cells with graphite anodes were subject to Li plating by being cycled at 5 Li-ion batteries suffer from aging reactions which limit their lifetime in applications.1,2 It is known that chemical reactions such as SEI growth on anodes and dissolution of cathode active material are accelerated with increasing temperature, following an Arrhenius-like behavior. [3][4][5] In contrast, Li deposition and subsequent reaction with electrolyte is usually observed after charging at low temperatures and/or high rates. 4,[6][7][8][9][10][11] Li deposition causes rapid capacity decay 4,11 and can significantly reduce cell safety. 12The reason for lithium deposition is anode polarization, which drops below 0 V vs. Li/Li + in the respective cases. 4,6 However, measuring the anode potential in full cells requires a reference electrode that is not present in commercial cells. Therefore, non-destructive methods for detection of Li deposition and quantification are under development by several groups. 7-10In order to validate non-destructive detection methods, one has to be able to detect Li chemically after cell opening. Petzl et al. recently used the reactivity of Li with water as a sign of metallic Li on graphite anodes. 7 In post-mortem analysis, the high reactivity of Li metal makes it challenging to open the cell in charged state, especially in the presence of deposited Li. Analysis of graphite anodes subject to Li deposition can be done using methods such as inductively coupled plasma spectroscopy (ICP) and atomic absorption spectroscopy (AAS), however, distinguishing between metallic Li and intercalated Li is not possible. Therefore, a quantification of Li deposition in postmortem analysis is not available in literature at the moment.Glow Discharge Optical Emission Spectroscopy (GD-OES) was introduced by Grimm in 1968 13 and later used as a standard method for characterization of non-porous metallic materials, e.g. in steel industry. Similar to X-ray photoelectron spectroscopy (XPS) depth profiling, GD-OES employs an inert gas (usually Ar) as discharge source to perform a depth-resolved elemental analysis sensitive to light elements like Li. XPS is, however, a surface-sensitive method while GD-OES can be applied through the whole electrode coating.Recently, GD-OES has been also applied to porous electrodes from Li-ion batteries by Saito et al.14 The technique was further developed by Takahara et al., focusing on reactive sputtering, Li quantification in the electrodes and analysis of surface deposition on graphite anode (SEI). 15-18The present study introduces a novel method to prove Li deposition on graphite anodes of Li-ion batteries by means of GD-OES depth profiling. For comparison, anodes from cells where Li plating is expected (cycling at low temperatures) are compared to anodes without Li plating but initial SEI formation (anodes from fresh cell). ExperimentalG...

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In Situ Detection of Lithium Plating on Graphite Electrodes by Electrochemical Calorimetry

Cited by 132 publications

References 23 publications

Electrochemical, Post-Mortem, and ARC Analysis of Li-Ion Cell Safety in Second-Life Applications

Electrochemical, Post-Mortem, and ARC Analysis of Li-Ion Cell Safety in Second-Life Applications

In-Situ Detection of Lithium Plating Using High Precision Coulometry

Detection of Li Deposition by Glow Discharge Optical Emission Spectroscopy in Post-Mortem Analysis

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