Operando X-ray photoelectron spectroscopy of solid electrolyte interphase formation and evolution in Li2S-P2S5 solid-state electrolytes

Wood, Kevin N.; Steirer, K. Xerxes; Hafner, Simon; Ban, Chunmei; Santhanagopalan, Shriram; Lee, Se-Hee; Teeter, Glenn

doi:10.1038/s41467-018-04762-z

Cited by 223 publications

(228 citation statements)

References 31 publications

Supporting

Mentioning

202

Contrasting

Order By: Relevance

“…The resistance of the β‐Li 3 PS 4 cell appears to fluctuate but tends toward higher resistance over cycling, in good accord with findings reported elsewhere for Li symmetric cells . This increasing resistance has been attributed to the formation of a passivating interphase composed of Li 2 S and Li 3 P . Because of this, β‐Li 3 PS 4 has been widely regarded as one of the most stable solid‐electrolytes with Li metal, by comparison to other well‐known materials .…”

Section: Resultssupporting

confidence: 87%

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

Kaup

Bazak

Vajargah

et al. 2020

Advanced Energy Materials

View full text Add to dashboard Cite

As potential next‐generation energy storage devices, solid‐state lithium batteries require highly functional solid state electrolytes. Recent research is primarily focused on crystalline materials, while amorphous materials offer advantages by eliminating problematic grain boundaries that can limit ion transport and trigger dendritic growth at the Li anode. However, simultaneously achieving high conductivity and stability in glasses is a challenge. New quaternary superionic lithium oxythioborate glasses are reported that exhibit high ion conductivity up to 2 mS cm−1 despite relatively high oxygen: sulfur ratios of more than 1:2, that exhibit greatly reduced H2S evolution upon exposure to air compared to Li7P3S11. These monolithic glasses are prepared from vitreous melts without ball‐milling and exhibit no discernable XRD pattern. Solid‐state NMR studies elucidate the structural entities that comprise the local glass structure which dictates fast ion conduction. Stripping/plating onto lithium metal results in very low polarization at a current density of 0.1 mA cm−2 over repeated cycling. Evaluation of the optimal glass composition as an electrolyte in an all‐solid‐state battery shows it exhibits excellent cycling stability and maintains near theoretical capacity for over 130 cycles at room temperature with Coulombic efficiency close to 99.9%, opening up new avenues of exploration for these quaternary compositions.

show abstract

Section: Resultssupporting

confidence: 87%

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

Kaup

Bazak

Vajargah

et al. 2020

Advanced Energy Materials

View full text Add to dashboard Cite

show abstract

“…1 The SEI can continue to evolve during cycling as uncontrolled side reactions occur, and in some cases SEI phases themselves might be redox-active. [2][3][4] The SEI can dramatically affect both battery performance and cycling stability. 5 Therefore, understanding the processes that lead to SEI formation and evolution is a necessary step toward engineering stable, long lasting, and safe LIBs.…”

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.

Self Cite

405

343

View full text Add to dashboard Cite

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.

show abstract

“…[177] The SEI growth could be modeled as a diffusion-controlled process with interface-controlled reaction predominating during the first few minutes. [187] Similar to the Li 7 P 3 S 11 , Li 3 PS 4 , and LGPS, the Li 2 S and Li 3 P were also the primary interphases for the Li 2 S-P 2 S 5 . Even though the amount was small, the surface of LGPS was degraded continuously because the SEI layer was not entirely electronically insulating.…”

Section: Origin Of the Interfacial Resistancementioning

confidence: 82%

“…Some binary systems such as LiI and Li 3 N belong to this group. [187] Copyright 2018, Springer Nature Publishing AG. The interphases formed will allow transport of electrons continuously, leading to self-charge of the batteries.…”

Section: Origin Of the Interfacial Resistancementioning

confidence: 99%

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Liu

et al. 2019

Advanced Energy Materials

View full text Add to dashboard Cite

The continuous depletion of fossil fuels, the increase of oil prices, and the need to decrease CO 2 emissions have stimulated intensive research on developing alternative renewable and clean energy sources. [1] Among these alternative energy sources, rechargeable Li-ion batteries (LIBs) are one of the promising candidates. To date, the LIBs basically consisting of a positive electrode (cathode), an electrolyte, and a negative electrode (anode) have widespread applications, such as portable electronic devices, pure electric vehicles (PEVs), and hybrid electric vehicles (HEVs). [2] The state-of-the-art electrolytes are usually the lithium salts (LiPF 6 , LiBF 4 , and LiCF 3 SO 3 ) dissolved in organic solvents, i.e., ethylene carbonate, propylene carbonate, polyethylene oxide, and dimethyl carbonate, [3] which exhibit excellent wetting of the electrodes and produce a fast transfer of Li + ions upon charging and discharging. However, they suffer from flammability, poor electrochemical stability, limited temperature range of operation, and low power density. [4] There is an ever-increasing demand for batteries with a higher energy and power density, although current LIBs offer volumetric and gravimetric energy densities up to 770 Wh L −1 and 260 Wh kg −1 , respectively. [5] To improve the energy/power density of LIBs, one way is to adopt high-potential cathode materials such as LiNi 0.5 Mn 1.5 O 4 (LNMO). The high-voltage plateau of LNMO (≈4.7 V vs Li/Li + ) makes its energy density 20-30% higher than the energy density of commercial LiCoO 2 and LiFePO 4 . [6] However, successful commercialization of the LNMO is restricted in high-energy LIBs due to electrolyte decomposition and side reaction of the cathodes and liquid electrolytes when operating at high voltages. [7,8] The other way to improve the energy/power density is to replace the conventional graphite anode with Li metal. The Li metal, with a low anode potential (−3.04 V vs standard hydrogen electrode) and high specific capacity (3862 mAh g −1 for the Li anode versus 372 mAh g −1 for the graphite anode), [9][10][11] has been considered as the "Holy Grail" of battery technologies. When paired with sulfur and oxygen, the theoretical energy density of Li-S (≈2567 Wh kg −1 ) and Li-O 2 (≈3505 Wh kg −1 ) batteries is far higher than the theoretical energy density of conventional LIBs (≈387 Wh kg −1 ). [12][13][14][15] When Li metal approaches the liquid electrolytes, however, unstable Li/electrolyte interface Rechargeable Li-ion batteries (LIBs) are electrochemical storage device widely applied in electric vehicles, mobile electronic devices, etc. However, traditional LIBs containing liquid electrolytes suffer from flammability, poor electrochemical stability, and limited operational temperature range. Replacement of the liquid electrolytes with inorganic solid-state electrolytes (SSEs) would solve this problem. However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted befor...

show abstract

Operando X-ray photoelectron spectroscopy of solid electrolyte interphase formation and evolution in Li2S-P2S5 solid-state electrolytes

Cited by 223 publications

References 31 publications

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity

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

Interfacial Incompatibility and Internal Stresses in All‐Solid‐State Lithium Ion Batteries

Contact Info

Product

Resources

About