Breaking Down a Complex System: Interpreting PES Peak Positions for Cycled Li-Ion Battery Electrodes

Lindgren, Fredrik; Rehnlund, David; Källquist, Ida; Nyholm, Leif; Edström, Kristina; Hahlin, Maria; Maibach, Julia

doi:10.1021/acs.jpcc.7b08923

Cited by 34 publications

(58 citation statements)

References 37 publications

(62 reference statements)

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“…The latter is very important, as this is, to the best of our knowledge, the first HAXPES evidence for the lithium-trapping effect. By comparing the positions of the peaks in Figure 4 with those reported in our previous work involving step-by-step lithiation of silicon, [23] it can be seen that the spectra for the 25th cycle match those previously obtained using a lithiation capacity of Adv. Energy Mater.…”

Section: Hard X-ray Photoelectron Spectroscopy (Haxpes) Analyses Of Ssupporting

confidence: 75%

“…After the first lithiation, a new peak due to the Li–Si alloy emerged at lower binding energies (see the yellow Li z Si peak in Figure ) in addition to the silicon peak. In the spectra for the cycled electrode, the silicon peak was denoted Li x Si to indicate that the electrode also contained some residual lithium yielding a shift toward lower binding energies . The latter shift should, incidentally, be coupled to the shift in the redox potential of the electrode to lower potentials expected for an increasing lithium concentration in the electrode (see Section ).…”

Section: Resultsmentioning

confidence: 99%

“…In the spectra for the cycled electrode, the silicon peak was denoted Li x Si to indicate that the electrode also contained some residual lithium yielding a shift toward lower binding energies. [23] The latter shift should, incidentally, be coupled to the shift in the redox potential of the electrode to lower potentials expected for an increasing lithium concentration in the electrode (see Section 2.1). After 25 and 50 cycles, the Li-Si alloy peak had clearly increased in size, indicating a build-up of residual lithium at the electrode surface that should not be present in the absence of the lithium-trapping effect.…”

Section: Hard X-ray Photoelectron Spectroscopy (Haxpes) Analyses Of Smentioning

confidence: 99%

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On the Capacity Losses Seen for Optimized Nano‐Si Composite Electrodes in Li‐Metal Half‐Cells

Lindgren

Rehnlund

Pan

et al. 2019

Advanced Energy Materials

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100

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While the use of silicon‐based electrodes can increase the capacity of Li‐ion batteries considerably, their application is associated with significant capacity losses. In this work, the influences of solid electrolyte interphase (SEI) formation, volume expansion, and lithium trapping are evaluated for two different electrochemical cycling schemes using lithium‐metal half‐cells containing silicon nanoparticle–based composite electrodes. Lithium trapping, caused by incomplete delithiation, is demonstrated to be the main reason for the capacity loss while SEI formation and dissolution affect the accumulated capacity loss due to a decreased coulombic efficiency. The capacity losses can be explained by the increasing lithium concentration in the electrode causing a decreasing lithiation potential and the lithiation cut‐off limit being reached faster. A lithium‐to‐silicon atomic ratio of 3.28 is found for a silicon electrode after 650 cycles using 1200 mAhg−1 capacity limited cycling. The results further show that the lithiation step is the capacity‐limiting step and that the capacity losses can be minimized by increasing the efficiency of the delithiation step via the inclusion of constant voltage delithiation steps. Lithium trapping due to incomplete delithiation consequently constitutes a very important capacity loss phenomenon for silicon composite electrodes.

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Section: Hard X-ray Photoelectron Spectroscopy (Haxpes) Analyses Of Ssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 99%

Section: Hard X-ray Photoelectron Spectroscopy (Haxpes) Analyses Of Smentioning

confidence: 99%

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On the Capacity Losses Seen for Optimized Nano‐Si Composite Electrodes in Li‐Metal Half‐Cells

Lindgren

Rehnlund

Pan

et al. 2019

Advanced Energy Materials

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100

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“…18,25 At the lower binding energy side, a new doublet at about 160.6 eV (2p 3/2 ) was observed when using Super C65, CNF or no additive in the cathode composite, stemming from the formation of Li 2 S. 29,30 Interestingly, the peaks related to PS 4 3À were shied by 0.4-0.5 eV to higher binding energies relative to the pristine state when Li 2 S was apparent. This may be due to charging or electronic interface effects during the measurement because of the insulating nature of Li 2 S. 31,32 Nevertheless, the distinct mechanisms leading to Li 2 S and SO x formation are yet to be resolved. We also note that the Ti 2p peaks showed some shi in binding energy aer cycling ( Fig.…”

Section: Resultsmentioning

confidence: 99%

Influence of electronically conductive additives on the cycling performance of argyrodite-based all-solid-state batteries

et al. 2020

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All-solid-state batteries (SSBs) are attracting widespread attention as next-generation energy storage devices, potentially offering increased power and energy densities and better safety than liquid electrolyte-based Li-ion batteries. Significant research efforts are currently underway to develop stable and high-performance bulk-type SSB cells by optimizing the cathode microstructure and composition, among others. Electronically conductive additives in the positive electrode may have a positive or negative impact on cyclability. Herein, it is shown that for high-loading (pelletized) SSB cells using both a size-and surface-tailored Ni-rich layered oxide cathode material and a lithium thiophosphate solid electrolyte, the cycling performance is best when low-surface-area carbon black is introduced.

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“…Also, as shown in a recent study, a buried interphase potential difference that increases with cycling has been observed that can cause quite large shifts-on the order of nearly 2 eV-in the C 1s peak associated with the SEI. 17 Furthermore, hydrocarbon species in the electrode at different stages of cycling (for example, those in a pristine electrode vs. those in an SEI) might not be the same, and therefore could have differing BEs.…”

Section: Introductionmentioning

confidence: 99%

XPS on Li-Battery-Related Compounds: Analysis of Inorganic SEI Phases and a Methodology for Charge Correction

Wood

Teeter

2018

ACS Appl. Energy Mater.

368

343

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Accurate identification of chemical phases associated with the electrode and solid-electrolyte interphase (SEI) is critical for understanding and controlling interfacial degradation mechanisms in lithium-containing battery systems. To study these critical battery materials and interfaces Xray photoelectron spectroscopy (XPS) is a widely used technique that provides quantitative chemical insights. However, due to the fact that a majority of chemical phases relevant to battery interfaces are poor electronic conductors, phase identification that relies primarily on absolute XPS core level binding-energies (BEs) can be problematic. Charging during XPS measurements leads to BE shifts that can be difficult to correct. These difficulties are often exacerbated by the coexistence of multiple Li-containing phases in the SEI with overlapping XPS core levels. To facilitate accurate phase identification of battery-relevant phases (and electronically insulating phases in general), we propose a straightforward approach for removing charging effects from XPS data sets. We apply this approach to XPS data sets acquired from six battery-relevant inorganic phases including lithium metal (Li 0 ), lithium oxide (Li2O), lithium peroxide (Li2O2), 2 lithium hydroxide (LiOH), lithium carbonate (Li2CO3) and lithium nitride (Li3N). Specifically, we demonstrate that BE separations between core levels present in a particular phase (e.g. BE separation between the O 1s and Li 1s core levels in Li2O) provides an additional constraint that can significantly improve reliability of phase identification. For phases like Li2O2 and LiOH where the Li-to-O ratios and BE separations are nearly identical, x-ray excited valence-band spectra can provide additional clues that facilitate accurate phase identification. We show that in-situ growth of Li2O on Li 0 provides a means for determining absolute core level positions, where are all charging effects are removed. Finally, as an exemplary case we apply the charge-correction methodology to XPS data acquired from a symmetric cell based on a Li2S-P2S5 solid electrolyte.This analysis demonstrates that accurately accounting for XPS BE shifts as a function of currentbias conditions can provide a direct probe of ionic conductivities associated with battery materials.

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Breaking Down a Complex System: Interpreting PES Peak Positions for Cycled Li-Ion Battery Electrodes

Cited by 34 publications

References 37 publications

On the Capacity Losses Seen for Optimized Nano‐Si Composite Electrodes in Li‐Metal Half‐Cells

On the Capacity Losses Seen for Optimized Nano‐Si Composite Electrodes in Li‐Metal Half‐Cells

Influence of electronically conductive additives on the cycling performance of argyrodite-based all-solid-state batteries

XPS on Li-Battery-Related Compounds: Analysis of Inorganic SEI Phases and a Methodology for Charge Correction

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