Correlation between lithium deposition on graphite electrode and the capacity loss for LiFePO 4 /graphite cells

Tan, Li; Zhang, Li; Qu, Qunting; Wan, Zhongming; Wang, Yan; Shen, Ming; Zheng, Honghe

doi:10.1016/j.electacta.2015.05.039

Cited by 53 publications

(25 citation statements)

References 44 publications

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“…51,52 Several researchers have suggested that SEI cracks and SEI reformation due to volume changes of the graphite anode during cycling operations are the major cause of lithium consumption. 28,53,54 Graphite anodes exhibit a largely linear expansion from 0% to 25% lithiation, only minor volume changes between 25% and 50% lithiation, and another linear expansion above 50% lithiation, where the LiC 6 phase formation begins. 52 Comparing this thickness behavior of lithiated graphite with the observed trends in capacity fade, an interdependency between graphite expansion and calendar aging can be disregarded: In the high SoC region above the central graphite peak, corresponding to a lithiation of the graphite anode greater than 50%, a constant capacity fade is observed.…”

Section: 45mentioning

confidence: 99%

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Calendar Aging of Lithium-Ion Batteries

Keil

Schuster

Wilhelm

et al. 2016

J. Electrochem. Soc.

458

288

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In this study, the calendar aging of lithium-ion batteries is investigated at different temperatures for 16 states of charge (SoCs) from 0 to 100%. Three types of 18650 lithium-ion cells, containing different cathode materials, have been examined. Our study demonstrates that calendar aging does not increase steadily with the SoC. Instead, plateau regions, covering SoC intervals of more than 20%-30% of the cell capacity, are observed wherein the capacity fade is similar. Differential voltage analyses confirm that the capacity fade is mainly caused by a shift in the electrode balancing. Furthermore, our study reveals the high impact of the graphite electrode on calendar aging. Lower anode potentials, which aggravate electrolyte reduction and thus promote solid electrolyte interphase growth, have been identified as the main driver of capacity fade during storage. In the high SoC regime where the graphite anode is lithiated more than 50%, the low anode potential accelerates the loss of cyclable lithium, which in turn distorts the electrode balancing. Aging mechanisms induced by high cell potential, such as electrolyte oxidation or transition-metal dissolution, seem to play only a minor role. To maximize battery life, high storage SoCs corresponding to low anode potential should be avoided.

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Section: 45mentioning

confidence: 99%

“…However, these studies usually considered only a few storage SoCs or storage voltages. Most of the studies examined only three different values or fewer, [18][19][20][21][22][23][24][25][26][27][28] and there is one study that investigated five SoCs from 20% * Electrochemical Society Member. z E-mail: peter.keil@tum.de to 100%.…”

mentioning

confidence: 99%

Calendar Aging of Lithium-Ion Batteries

Keil

Schuster

Wilhelm

et al. 2016

J. Electrochem. Soc.

458

288

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“…Sometimes, metallic lithium, although still active, can be electronically disconnected from the electrode and is thus unusable ("dead z E-mail: arnaud.delaille@cea.fr lithium"). 4,5,10,17 This lithium loss contributes to progressive and irreversible capacity fading.Graphite is one of the most common negative electrodes and presents plateaus of intercalation / deintercalation between 0.05 and 0.1 V vs. Li/Li + , 32-35 while below 0 V vs Li/Li + lithium metal forms. The detection of metallic lithium deposition is possible by measuring the potential of the negative electrode using a reference electrode.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] In the literature, it is reported that the mechanism of lithium deposition generally occurs during the charge at low temperatures and/or at high current-rates. The intercalation of lithium ions into the structure of the negative electrode is in competition with the deposition of metallic lithium on top of the Solid Electrolyte Interphase (SEI).…”

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confidence: 99%

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Effects of Biphenyl Polymerization on Lithium Deposition in Commercial Graphite/NMC Lithium-Ion Pouch-Cells during Calendar Aging at High Temperature

Matadi

Géniès

Delaille

et al. 2017

J. Electrochem. Soc.

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Metallic lithium deposition is a typical aging mechanism observed in lithium-ion cells at low temperature and/or at high charge rate. Lithium dendrite growth not only leads to strong capacity fading, it also causes safety concerns such as short-circuits in the cell. In applications such as electric vehicles, the use of lithium-ion batteries combines discharging, long rest time and charging phases. It is foremost a matter of lifetime and safety from the perspective of the consumer or the investor. This study presents the post-mortem analyses of commercial 16 Ah Graphite/NMC (Nickel Manganese Cobalt layered oxide) Li-ion pouch cells. The cells were degraded by calendar aging at high temperature with or without periodic capacity tests. Unexpected local depositions of metallic lithium were confirmed on graphite electrodes by Nuclear Magnetic Resonance (NMR). Biphenyl, a monomer additive present in the liquid electrolyte, generates gas during its polymerization reaction occurring at high temperature and at high state of charge. As a result, dry-out areas are present between the electrodes leading to high impedance regions and no charge transfer between the electrodes. It is at the border of these areas that lithium metal is deposited. Lithium-ion batteries have the particularity of addressing applications as diverse as mobile electronic devices, electric vehicles or stationary applications of renewable energy. The use of rechargeable electrochemical cells is first and foremost a question of autonomy, lifetime and safety.1-3 So it is necessary to further increase the current performance of lithium-ion batteries.Deposition of metallic lithium or "lithium plating" is one of the aging mechanisms that is limiting the lifetime of lithium-ion batteries. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] In the literature, it is reported that the mechanism of lithium deposition generally occurs during the charge at low temperatures and/or at high current-rates. The intercalation of lithium ions into the structure of the negative electrode is in competition with the deposition of metallic lithium on top of the Solid Electrolyte Interphase (SEI). The morphology of the negative electrode, the porosity, the conductivity of the electrolyte and the state of lithiation are parameters to be considered. 8 This aging mechanism depends on intrinsic criteria of the components of the cell (active material, electrodes and electrolyte composition [21][22][23][24][25][26][27][28][29][30] ) and extrinsic to the system (temperature and charging current).Contact between the deposited lithium and the electrolyte (above the surface of the SEI) leads to the oxidation of lithium to form species such as ROCO 2 Li, Li 2 CO 3 or LiF. 15 The deposited lithium becomes isolated and electrochemically inactive and cannot participate in the electrochemical process at the electrodes. The deposit can grow in height from graphite particles and form dendrites which can pass through the separator and cause short circuit. This phenomena in combinatio...

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Toward Sustainable Lithium Iron Phosphate in Lithium‐Ion Batteries: Regeneration Strategies and Their Challenges

Yan,

Qian,

et al. 2024

Adv Funct Materials

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In recent years, the penetration rate of lithium iron phosphate batteries in the energy storage field has surged, underscoring the pressing need to recycle retired LiFePO4 (LFP) batteries within the framework of low carbon and sustainable development. This review first introduces the economic benefits of regenerating LFP power batteries and the development history of LFP, to establish the necessity of LFP recycling. Then, the entire life cycle process and failure mechanism of LFP are outlined. The focus is on highlighting the advantages of direct recycling technology for LFP materials. Directly regenerating LFP materials is a very promising solution. Directly regenerating spent LFP (S‐LFP) materials can not only protect the environment and save resources, but also directly add lithium atoms to the vacancies of missing lithium atoms to repair S‐LFP materials. At the same time, simply supplementing lithium to repair S‐LFP simplifies the recovery process and improves economic benefits. The status of various direct recycling methods is then reviewed in terms of the regeneration process, principles, advantages, and challenges. Additionally, it is noted that direct recycling is currently in its early stages, and there are challenges and alternative directions for its development.

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Correlation between lithium deposition on graphite electrode and the capacity loss for LiFePO 4 /graphite cells

Cited by 53 publications

References 44 publications

Calendar Aging of Lithium-Ion Batteries

Calendar Aging of Lithium-Ion Batteries

Effects of Biphenyl Polymerization on Lithium Deposition in Commercial Graphite/NMC Lithium-Ion Pouch-Cells during Calendar Aging at High Temperature

Toward Sustainable Lithium Iron Phosphate in Lithium‐Ion Batteries: Regeneration Strategies and Their Challenges

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