In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO2

Patridge, Christopher J.; Love, Corey T.; Swider‐Lyons, Karen; Twigg, M. E.; Ramaker, David E.

doi:10.1016/j.jssc.2013.04.008

Cited by 49 publications

(49 citation statements)

References 69 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Figure 5 shows selected elemental scans for two cells cycled for 25 and 50 cycles. These cells performed comparable to cells with nanoscale LiCoO 2 [18] in lithium salt-containing electrolyte, showing similar initial discharge capacity and relative capacity fade, with capacities of 20 mAh·g −1 after 50 cycles as shown by the electrochemical data in the Supporting Information, Figure S2. These fade rates are however much faster than typical micron scale LiCoO 2 used in commercial cells [18].…”

Section: Resultsmentioning

confidence: 55%

“…4f, it is clear CsClO 4 dominates near the outer surface at the electrolyte/EDL interface. The large percentage can be attributed to the large surface area (morphology previously characterized [18]) of the n-LiCoO 2 . In Fig.…”

Section: Resultsmentioning

confidence: 85%

“…Cathode slurries were prepared using previously prepared nanoscale LiCoO 2 [18] (n-LiCoO 2 ) of approximately 40 nm diameter, conductive carbon (Timcal Super P), and polyvinlyidene fluoride (PVDF) dissolved in N-methylpyrrolidinone (NMP) with weight ratios of 80:10:10. Aqueous electrode slurries using a non-fluorinated binder, sodium carboxymethyl cellulose (NaCMC Aldrich M w : 90, 000), were introduced at the same weight ratio as PVDF.…”

Section: Electrochemical Cell Fabrication and Galvanostatic Cyclingmentioning

confidence: 99%

“…Individual scans took approximately 30 min to collect near edge XANES and extended region EXAFS absorption data. Several scans (15)(16)(17)(18)(19)(20) were accumulated to reduce noise. All X-ray absorption spectroscopy (XAS) data were processed with ATHENA [34] and standard XANES fitting with various rubidium standard XAS scans carried out using the linear combination fitting function of ATHENA.…”

Section: Electrochemical Cell Fabrication and Galvanostatic Cyclingmentioning

confidence: 99%

“…The difficulties with characterizing the electrode/electrolyte interphases has prompted the use of numerous techniques to elucidate aspects of the solid electrolyte interphase (SEI) [1] including X-ray photoelectron spectroscopy (XPS) [2][3][4][5][6], infrared spectroscopy (FTIR) [6][7][8], electrochemical impedance spectroscopy (EIS) [9][10][11][12][13], nuclear magnetic resonance 7 Li (NMR) [14][15][16][17], Xray absorption spectroscopy (XAS) [18][19][20][21], electron microscopy [22], Raman spectroscopy [23], ellipsometry [24], and several theoretical approaches [25][26][27]. The electrolyte decomposition layer (EDL) is the cathode counterpart to the SEI layer on the anode although its function is not required for intercalation stability; its origin is rooted in electrochemical decomposition of electrolyte salt and solvent on the active positive electrode surface.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Utilization of heavy alkali dopants as a beacon to study the cathode electrolyte decomposition layer in lithium-ion batteries

Patridge

Love

Ramaker

2015

Ionics

Self Cite

View full text Add to dashboard Cite

We introduce low levels of CsClO 4 and RbClO 4 into the electrolyte of LiCoO 2 electrochemical half-cells to probe the composition of the passivation film on the surface of the cathode, the electrolyte decomposition layer (EDL). The advantages of these heavy alkali dopants lie in their large ionic radii, which limit intercalation, yet their strong light scattering cross-section creates a beacon that highlights the formation of products near the cathode surface. Detailed surface analysis and depth profiling with X-ray photoelectron spectroscopy, and bulk analysis utilizing X-ray absorption spectroscopy, show evidence for the formation of Cs/Rb compounds, such as carbonates, halides, and perchlorates, similar to those formed by lithium in previous studies, but also reveal the significantly reduced mobility of the Cs/Rb relative to Li in the non-uniform EDL. This unique approach could open several presently untapped techniques to gather new information on the EDL in Li-ion batteries.

show abstract

Section: Resultsmentioning

confidence: 55%

Section: Resultsmentioning

confidence: 85%

Section: Electrochemical Cell Fabrication and Galvanostatic Cyclingmentioning

confidence: 99%

Section: Electrochemical Cell Fabrication and Galvanostatic Cyclingmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Utilization of heavy alkali dopants as a beacon to study the cathode electrolyte decomposition layer in lithium-ion batteries

Patridge

Love

Ramaker

2015

Ionics

Self Cite

View full text Add to dashboard Cite

show abstract

Novel XAS Techniques for Probing Fuel Cells and Batteries

Ramaker

2016

X‐Ray Absorption and X‐Ray Emission Spectroscopy

View full text Add to dashboard Cite

The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium‐Ion Battery Cathode Materials

Wang

Fan

et al. 2020

Adv Funct Materials

View full text Add to dashboard Cite

Following the fundamental research conducted by J. B. Goodenough, the important role of electron localization induced by elemental substitution is studied. The size and electron negativity of host and substituting ions are two important factors in tuning material properties such as local structure and transition metal (TM) oxygen covalency. However, another factor, electron localization, which is widely studied in catalyst research but largely overlooked for battery materials, deserves systematic studies. A combined investigation using synchrotronbased X‐ray spectroscopy and theoretical calculations is carried out on the Li‐Co‐Mn‐O model system in which the substituting cation Mn4+, with its 3d3 electronic structure, is used as a promoter for electron localization. Results indicate that electron localization greatly influences the CoO bond by making it less covalent, which increases the delithiation voltage. It is also found that during charge/discharge, electron localization tends to make TM K‐edge X‐ray absorption near edge spectroscopy (XANES) spectra show a more “rigid shift” behavior while electron delocalization makes the XANES exhibit a “shape change.” It clearly explains why the K‐edge XANES data of some TM oxides show no “rigid shift” while the nominal valence states changed. This work highlights the importance of electron localization with guidance for XANES interpretation.

show abstract

In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO2

Cited by 49 publications

References 69 publications

Utilization of heavy alkali dopants as a beacon to study the cathode electrolyte decomposition layer in lithium-ion batteries

Utilization of heavy alkali dopants as a beacon to study the cathode electrolyte decomposition layer in lithium-ion batteries

Novel XAS Techniques for Probing Fuel Cells and Batteries

The Role of Electron Localization in Covalency and Electrochemical Properties of Lithium‐Ion Battery Cathode Materials

Contact Info

Product

Resources

About