Is the Solid Electrolyte Interphase an Extra-Charge Reservoir in Li-Ion Batteries?

Rezvani, Seyed Javad; Gunnella, R.; Witkowska, Agnieszka; Mueller, Franziska; Pasqualini, Marta; Nobili, Francesco; Passerini, Stefano; Cicco, Andrea Di

doi:10.1021/acsami.6b12408

Cited by 76 publications

(81 citation statements)

References 42 publications

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“…The profile in Figure shows that there is a large irreversible capacity loss during the first cycle with a Coulombic efficiency of 60 %, which is in agreement with the efficiency values of 61–64 %, previously reported for this type of materials during the first discharge/charge cycle ,. The higher value of the experimental discharge capacity (1140 mAh g −1 ) with respect to the theoretical one has already been observed for transition metal oxides and it can be explained by the electrolyte decomposition with the formation of the SEI, the lithiation of the carbon coating and carbon black or the formation of a polymer‐gel like film in transition metal oxide electrodes ,,…”

Section: Resultssupporting

confidence: 89%

“…For ZnFe 2 O 4 −C anode material, different components such as polyethylene oxide, organic alkyl carbonate species were detected by Raman spectroscopy, and also Li 2 CO 3 and LiF by X‐ray absorption (XAS) and X‐ray photoemission spectroscopy (XPS) ,,…”

Section: Resultsmentioning

confidence: 99%

“…The detection of these species by Raman spectroscopy was associated with a temporary surface enhancement of the Raman signal from metallic zinc nanoparticles that resulted from the reduction of ZnFe 2 O 4 during the conversion reaction at a potential that coincided with SEI formation . The SEI formed on ZnFe 2 O 4 −C was also investigated by X‐ray based techniques (e. g., XAS and XPS) . These studies reported the formation of a carbonate layer that evolves through different processes during the discharge cycle.…”

Section: Introductionmentioning

confidence: 99%

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In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn_0.9Fe_0.1O Anode for Lithium‐Ion Batteries

Cabo‐Fernández

Bresser

Braga

et al. 2018

Batteries & Supercaps

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Carbon‐coated Zn0.9Fe0.1O is a promising anode material for lithium‐ion batteries with good cycling performance and a theoretical specific capacity of 966 mAh g−1, as a result of the combined conversion‐alloying reaction during lithiation. The solid electrolyte interphase (SEI) formed on this electrode was investigated by in‐situ Raman spectroscopy and in‐situ shell‐isolated nanoparticles for enhanced Raman spectroscopy (SHINERS) during the first discharge/charge cycle. The spectra collected via in‐situ Raman spectroscopy showed that the carbon coating is also (de)lithiated and it remains mechanically intact after the first complete cycle. There was no evidence of peaks related to the SEI due to the absence of surface enhancement of the Raman effect in this material, as was previously observed for carbon‐coated ZnFe2O4. However, bands assigned to polyethylene oxide species (PEO) and different lithium alkyl carbonate compounds (i. e., ROCO2Li, ROLi and RCOOLi) from the SEI were observed via SHINERS. The enhancement of the Raman effect by Au−SiO2 core‐shell nanoparticles allows the detection of surface films at potentials at which the SEI is formed and their chemical composition, which is not possible otherwise due to the intrinsically weak scattering process. Therefore, these results show that the SHINERS technique is a powerful method to investigate the structural evolution of the electrode material with potential and interfacial reactions on lithium‐ion batteries.

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Section: Resultssupporting

confidence: 89%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn_0.9Fe_0.1O Anode for Lithium‐Ion Batteries

Cabo‐Fernández

Bresser

Braga

et al. 2018

Batteries & Supercaps

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“…[157][158][159][160][161] The decomposition of the organic electrolyte at the electrode surface forms a protective SEI, which allows the cell stability over a broad range of potential. [157][158][159][160][161] The decomposition of the organic electrolyte at the electrode surface forms a protective SEI, which allows the cell stability over a broad range of potential.…”

Section: Solid Electrolyte Interphasementioning

confidence: 99%

High‐Energy Aqueous Lithium Batteries

Eftekhari¹

2018

Advanced Energy Materials

152

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research, aqueous electrolytes were occasionally employed for the investigation of cathode materials instead of the conventional nonaqueous electrolytes. [9,10] It was discussed that the simplicity of an aqueous electrolyte provides a better opportunity for the fundamental studies of the process of intercalation/deintercalation of Li-ions as opposed to the nonaqueous electrolytes. For instance, although the formation of solid electrolyte interphase (SEI) is of utmost importance for the cyclability of LIB, the significant role of the electrolyte does not allow to exclusively study the electrochemical behavior of the electrode material under consideration. The current research has specifically targeted the development of ARLBs, but in practice, most of the recent papers have followed the same line of research in investigating a limited range of cathode and anode materials in the same aqueous electrolytes. [11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] A possible reason is that the key advantage of ARLBs was low cost, and thus, the focus was limited to a few inexpensive materials (e.g., lithium salts). Aqueous electrolytes are definitely excellent choices for the fundamental studies of electrode materials, but the practical development of ARLBs needs overcoming the key obstacles rather than finding more cathode materials.In any case, aqueous electrolytes were occasionally used during the 2000s by various research groups, but there was no vivid plan for the development of ARLBs. These works have been extensively reviewed before, [29][30][31][32][33] and it is not aimed to repeat the general works on aqueous electrolytes here. During the recent years, new opportunities have been introduced, which can extend the stable potential window of aqueous electrolyte to the range of 3-4 V. Upon this advancement, aqueous electrolytes can fairly compete with the conventional nonaqueous electrolytes for the fabrication of cheaper and safer LIBs. On the other hand, novel designs such as self-healing [34] or flexible [16,35,36] ARLBs have paved the path for new practical potentials of aqueous electrolytes. The present paper specifically focuses on the recent advancements and attempts to foster the strategy of research to shed light on the pathway of this emerging area of research. Two factors are directly responsible for achieving a high energy density, the specific capacity, and the cell voltage. Since the former is not massively controlled by the electrolyte and the specific capacity of most electroactive Owing to the high voltage of lithium-ion batteries (LIBs), the dominating electrolyte is non-aqueous. The idea of an aqueous rechargeable lithium battery (ARLB) dates back to 1994, but it had attracted little attention due to the narrow stable potential window of aqueous electrolytes, which results in low energy density. However, aqueous electrolytes were employed during the 2000s for the fundamental studies of electrode materials in the absence of side reactions such as the decomposition of organic spec...

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“…The NCM-NC hybrids have ah igherc apacity retention of 1034.6 mAh g À1 ,c ompared with those of the M-NFs and NiÀCo skeletons, and the Coulombic efficiency of the NCM-NC hybrid is 96.3 %i nt he second cycle. [49] 4) The highers pecific capacity mayo riginate from the contributiono ft he hollow NiÀCo skeletons (Figure S7 bi nt he Supporting Information). Thisf ading phenomenoni sm ainly attributed to the accumulation of lithiation-induced stress, volume variation, and pulverization of active materials due to mechanical and chemical degradation of the electrodes.…”

Section: Resultsmentioning

confidence: 99%

Hierarchical Hollow‐Nanocube Ni−Co Skeleton@MoO₃/MoS₂ Hybrids for Improved‐Performance Lithium‐Ion Batteries

Hou

Liu

et al. 2020

Chemistry A European J

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Improving the performance of anode materials for lithium-ion batteries (LIBs) is ah otly debated topic. Herein, hollow NiÀCo skeleton@MoS 2 /MoO 3 nanocubes (NCM-NCs), with an average size of about1 93 nm, have been synthesized through af acile hydrothermal reaction. Specifically, MoO 3 /MoS 2 composites are grown on NiÀCo skeletons derived from nickel-cobaltP russian blue analogue nanocubes (NiÀCo PBAs). The NiÀCo PBAs were synthesized through a precipitation method and utilized as self-templates that provided al arger specific surface area for the adhesion of MoO 3 /MoS 2 composites. According to Raman spectroscopy results,a s-obtained defect-richM oS 2 is confirmed to be a metallic 1T-phase MoS 2 .F urthermore, the average particle size of NiÀCo PBAs ( % 43 nm) is only about one-tenth of the previously reported particles ize ( % 400 nm). If assessed as anodes of LIBs, the hollow NCM-NC hybrids deliver an excellent rate performance and superiorc ycling performance (with an initial discharge capacity of 1526.3 mAh g À1 and up to 1720.6 mAh g À1 after 317 cycles under ac urrent density of 0.2 Ag À1 ). Meanwhile, ultralong cycling life is retained, even at high current densities (776.6 mAh g À1 at 2Ag À1 after 700 cycles and 584.8 mAh g À1 at 5Ag À1 after 800 cycles). Moreover,a tarate of 1Ag À1 ,t he average specific capacity is maintained at 661 mAh g À1 .T hus,t he hierarchical hollow NCM-NC hybridsw ith excellent electrochemical performance are ap romising anodem aterial for LIBs.[a] J.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Is the Solid Electrolyte Interphase an Extra-Charge Reservoir in Li-Ion Batteries?

Cited by 76 publications

References 42 publications

In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn_0.9Fe_0.1O Anode for Lithium‐Ion Batteries

In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn_0.9Fe_0.1O Anode for Lithium‐Ion Batteries

High‐Energy Aqueous Lithium Batteries

Hierarchical Hollow‐Nanocube Ni−Co Skeleton@MoO₃/MoS₂ Hybrids for Improved‐Performance Lithium‐Ion Batteries

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Is the Solid Electrolyte Interphase an Extra-Charge Reservoir in Li-Ion Batteries?

Cited by 76 publications

References 42 publications

In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn0.9Fe0.1O Anode for Lithium‐Ion Batteries

In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn0.9Fe0.1O Anode for Lithium‐Ion Batteries

High‐Energy Aqueous Lithium Batteries

Hierarchical Hollow‐Nanocube Ni−Co Skeleton@MoO3/MoS2 Hybrids for Improved‐Performance Lithium‐Ion Batteries

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In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn_0.9Fe_0.1O Anode for Lithium‐Ion Batteries

In‐Situ Electrochemical SHINERS Investigation of SEI Composition on Carbon‐Coated Zn_0.9Fe_0.1O Anode for Lithium‐Ion Batteries

Hierarchical Hollow‐Nanocube Ni−Co Skeleton@MoO₃/MoS₂ Hybrids for Improved‐Performance Lithium‐Ion Batteries