Direct in situ observation and explanation of lithium dendrite of commercial graphite electrodes

Guo, Zhan‐Sheng; Zhu, Jianyu; Feng, Jian‐Jun; Du, Shiyu

doi:10.1039/c5ra13289d

Cited by 101 publications

(86 citation statements)

References 40 publications

(76 reference statements)

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“…3,23 Therefore, dissolution starting at the tip and moving down towards the electrode, which is observed in CTAB solution, means the entire dendrite is removed. The formation of "dead" silver during the dendrite dissolution in an aqueous AgNO 3 solution (in the absence of CTAB surfactant) is also shown in the Supporting Figure S9.…”

Section: Resultsmentioning

confidence: 99%

CTAB-Influenced Electrochemical Dissolution of Silver Dendrites

et al. 2016

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Dendrite formation on the electrodes of a rechargeable battery during the charge-discharge cycle limits its capacity and application due to short-circuits and potential ignition. However, understanding of the underlying dendrite growth and dissolution mechanisms is limited. Here, the electrochemical growth and dissolution of silver dendrites on platinum electrodes immersed in an aqueous silver nitrate (AgNO3) electrolyte solution was investigated using in situ liquid-cell transmission electron microscopy (TEM). The dissolution of Ag dendrites in an AgNO3 solution with added cetyltrimethylammonium bromide (CTAB) surfactant was compared to the dissolution of Ag dendrites in a pure aqueous AgNO3 solution. Significantly, when CTAB was added, dendrite dissolution proceeded in a step-by-step manner, resulting in nanoparticle formation and transient microgrowth stages due to Ostwald ripening. This resulted in complete dissolution of dendrites and "cleaning" of the cell of any silver metal. This is critical for practical battery applications because "dead" lithium is known to cause short circuits and high-discharge rates. In contrast to this, in a pure aqueous AgNO3 solution, without surfactant, dendrites dissolved incompletely back into solution, leaving behind minute traces of disconnected silver particles. Finally, a mechanism for the CTAB-influenced dissolution of silver dendrites was proposed based on electrical field dependent binding energy of CTA(+) to silver.

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Section: Resultsmentioning

confidence: 99%

CTAB-Influenced Electrochemical Dissolution of Silver Dendrites

et al. 2016

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“…[ 1 -3 During subsequent charging/discharging cycles, the inhomogeneous growth of the SEI layer can lead to Li dendrite formation, which can eventually induce short circuiting and self-ignition of the cell. [4][5][6] To prevent such safety concerns, Li 4 Ti 5 O 12 has been proposed as a replacement for low voltage anodes. Its electrochemical activity, based on the Ti 4+ /Ti 3+ couple (1.55 V vs. Li metal), is higher than the one of conventional carbon negatives electrodes which prevents the growth of Li dendrites.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical performances and gassing behavior of high surface area titanium niobium oxides

et al. 2016

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A solvothermal synthesis is developed to build a 3D network of nanoparticles, enhancing the electrochemical performances of both TiNb 2 O 7 and Ti 2 Nb 10 O 29 , especially at high current densities, with up to 190 mAh g -1 at 10C. A set of 11 mAh pouch cells combining the nanosized TiNb 2 O 7 with LiMn 1.5 Ni 0.5 O 4 is tested and is the first to be reported for this material. Soft shell cells are used, not only to evaluate the electrochemical performances of this oxide in a larger scale battery, but also to assess its gassing behavior, a well-known limitation for application of Li 4 Ti 5 O 12 in hybrid electric vehicles. In order to evaluate the sole contribution of TiNb 2 O 7 to the swelling, an additional set of soft shell TiNb 2 O 7 /Li(Ni 1/3 Mn 1/3 Co 1/3 )O 2 cells is assembled and stored at 45 ºC in a charged state. A higher swelling behavior is observed for TiNb 2 O 7 in comparison to Li 4 Ti 5 O 12 ; a clear trend also appears between surface area of the oxide and amount of gassing. The swelling of TiNb 2 O 7 or Ti 2 Nb

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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.…”

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confidence: 99%

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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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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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Direct in situ observation and explanation of lithium dendrite of commercial graphite electrodes

Abstract: In situ observed electrodeposition and dissolution of lithium dendrite of commercial graphite electrode.

Cited by 101 publications

References 40 publications

CTAB-Influenced Electrochemical Dissolution of Silver Dendrites

CTAB-Influenced Electrochemical Dissolution of Silver Dendrites

Electrochemical performances and gassing behavior of high surface area titanium niobium oxides

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

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