Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review

Zhan, Chun; Wu, Tianpin; Lü, Jun; Amine, Khalil

doi:10.1039/c7ee03122j

Cited by 660 publications

(620 citation statements)

References 127 publications

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“…7,14 These reactions may be paired with electrode transformations later in cell life including changes to the positive electrode surface structure from layered to spinel 1,15 and transition metal dissolution from the positive electrode followed by deposition on the negative electrode. 16 Here, analysis methods are presented that can track some of these changes to Li-ion cells to ultimately measure the impact of these reactions throughout cell lifetime. First, a simple, modified extraction method compared to that presented by Petibon et al 17 is introduced to obtain pure electrolyte from pouch cells.…”

mentioning

confidence: 99%

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Thompson

Stone

Eldesoky

et al. 2018

J. Electrochem. Soc.

101

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A set of LiNi 0.5 Mn 0.3 Co 0.2 O 2 /graphite lithium-ion cells underwent 750 charge-discharge cycles during about 8 months at 55 • C to upper cutoff potentials of 4.0, 4.1, 4.2, 4.3, and 4.4 V. The electrolyte in these cells was extracted using a centrifuge method and studied using gas chromatography/mass spectrometry to determine the changes to the solvents and by inductively coupled plasma-mass spectrometry to determine the changes to the salt content in the electrolyte. The negative electrodes from the cells were harvested and studied by micro-X-ray fluorescence to quantify the amount of transition metals which migrated from the positive electrode to the negative electrode during the testing. Emphasis is given to a detailed description of the quantitative methods used in the hope that others will adopt them in similar studies of different types of aged lithium-ion cells. The cells studied here initially had 1.1 molal LiPF 6 ethylene carbonate (EC): ethyl methyl carbonate (EMC) (3:7 by weight) electrolyte. The aged cells showed increasing amounts of dimethyl carbonate and diethyl carbonate created by transesterification as the upper cutoff potential increased. Only extremely small amounts of Mn, less than 0.1% of the total Mn in the positive electrode, were found on the negative electrode after this aggressive testing. Lithium-ion batteries are currently used in a wide range of applications: cell phones, power tools, vehicles and even grid energy storage.

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confidence: 99%

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Thompson

Stone

Eldesoky

et al. 2018

J. Electrochem. Soc.

101

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“…The first coulombic efficiency of the LNMO/G‐0 cell is 63%, and the values of LNMO/G‐2.5, LNMO/G‐1, and LNMO/G‐0.5 cells are increased to nearly 71%. Obviously, LNMO/graphite full cells have lower first coulombic efficiency than graphite/Li half cells, which is related to the oxidative decomposition of the electrolyte at a high voltage on the LNMO electrode . Cycling performance of these full cells is shown in Figure b.…”

Section: Results Of Surface Element Analysis On the Anodes Extractedmentioning

confidence: 99%

Nano‐Sized AlPO₄ Coating Layer on Graphite Powder to Improve the Electrochemical Properties of High‐Voltage Graphite/LiNi_0.5Mn_1.5O₄ Li‐Ion Cells

Zeng

Fang

et al. 2019

Energy Tech

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A high‐voltage graphite/LiNi0.5Mn1.5O4 (LNMO) system is a promising candidate for next‐generation Li‐ion batteries with a high energy density. However, it has the drawback of severe capacity fading caused by the consumption of active Li+ ions due to the reduction of the products of electrolyte oxidation and LNMO dissolution from the LNMO cathode on the graphite anode. Herein, graphite coated with different amounts of AlPO4 (0.5, 1, and 2.5 wt%) is prepared by an electrostatic attraction combined with a precipitation conversion method, and used as an anode for the LNMO/graphite full cell. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and elemental mapping images show that AlPO4 disperses homogeneously on the surface of graphite, and its thickness is between 10 and 30 nm. Electrochemical measurement results show that LNMO/AlPO4@graphite cells show better cycling stability and higher coulombic efficiency than the LNMO/graphite cell. Among them, the LNMO/0.5 wt% AlPO4@graphite cell shows the best cycling stability. By combining all the analytical results, the improvement mechanism of LNMO/AlPO4@graphite cells is mainly that the side reactions that consume the active Li+ ions are greatly reduced because the AlPO4 coating can block the migration of the products of electrolyte oxidation and LNMO dissolution to the graphite.

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“…However, the practical use of OLO is still hindered by the following challenges: i) initial irreversible capacity loss is large due to the extraction of lithium and oxygen ions from monoclinic Li 2 MnO 3 at charge voltages above 4.5 V (vs Li/Li + ), ii) consequent layered‐to‐spinel phase transition occurs, leading to structural instability and poor electrochemical reversibility during charge/discharge cycling, iii) rate capability is poor due to lower electronic conductivity (≈10 −9 S cm −1 ) than those of conventional cathode materials, and iv) interfacial side reactions occur with liquid electrolytes, which is accompanied by the transition metal dissolution from the OLO, resulting in rapid decline of cycling capacity …”

Section: Introductionmentioning

confidence: 99%

Ecofriendly Chemical Activation of Overlithiated Layered Oxides by DNA‐Wrapped Carbon Nanotubes

Kim

Park

et al. 2020

Advanced Energy Materials

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Despite their exceptionally high capacity, overlithiated layered oxides (OLO) have not yet been practically used in lithium‐ion battery cathodes due to necessary toxic/complex chemical activation processes and unsatisfactory electrochemical reliability. Here, a new class of ecofriendly chemical activation strategy based on amphiphilic deoxyribose nucleic acid (DNA)‐wrapped multiwalled carbon nanotubes (MWCNT) is demonstrated. Hydrophobic aromatic bases of DNA have a good affinity for MWCNT via noncovalent π–π stacking interactions, resulting in core (MWCNT)‐shell (DNA) hybrids (i.e., DNA@MWCNT) featuring the predominant presence of hydrophilic phosphate groups (coupled with Na+) in their outmost layers. Such spatially rearranged Na+–phosphate complexes of the DNA@MWCNT efficiently extract Li+ from monoclinic Li2MnO3 of the OLO through cation exchange reaction of Na+–Li+, thereby forming Li4Mn5O12‐type spinel nanolayers on the OLO surface. The newly formed spinel nanolayers play a crucial role in improving the structural stability of the OLO and suppressing interfacial side reactions with liquid electrolytes, eventually providing significant improvements in the charge/discharge kinetics, cyclability, and thermal stability. This beneficial effect of the DNA@MWCNT‐mediated chemical activation is comprehensively elucidated by an in‐depth structural/electrochemical characterization.

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Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review

Abstract: This paper reviews the research activities on the mechanistic understanding and solutions to overcome the TM DMD process, from the earliest discoveries to the latest progress.

Cited by 660 publications

References 127 publications

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Nano‐Sized AlPO₄ Coating Layer on Graphite Powder to Improve the Electrochemical Properties of High‐Voltage Graphite/LiNi_0.5Mn_1.5O₄ Li‐Ion Cells

Ecofriendly Chemical Activation of Overlithiated Layered Oxides by DNA‐Wrapped Carbon Nanotubes

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Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review

Abstract: This paper reviews the research activities on the mechanistic understanding and solutions to overcome the TM DMD process, from the earliest discoveries to the latest progress.

Cited by 660 publications

References 127 publications

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Quantifying Changes to the Electrolyte and Negative Electrode in Aged NMC532/Graphite Lithium-Ion Cells

Nano‐Sized AlPO4 Coating Layer on Graphite Powder to Improve the Electrochemical Properties of High‐Voltage Graphite/LiNi0.5Mn1.5O4 Li‐Ion Cells

Ecofriendly Chemical Activation of Overlithiated Layered Oxides by DNA‐Wrapped Carbon Nanotubes

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Nano‐Sized AlPO₄ Coating Layer on Graphite Powder to Improve the Electrochemical Properties of High‐Voltage Graphite/LiNi_0.5Mn_1.5O₄ Li‐Ion Cells