XPS Investigation of Surface Reactivity of Electrode Materials: Effect of the Transition Metal

Andreu, Nathalie; Flahaut, Delphine; Dedryvère, Rémi; Minvielle, Marie; Martínez, Hervé; Gonbeau, Danielle

doi:10.1021/am5089764

Cited by 123 publications

(119 citation statements)

References 33 publications

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“…The S 2p spectra also include an S 2p doublet of RSO 2 Li and Li 2 SO 3 at 166.2 eV, which results from the further reduction of the SO 3 complexes on the lithiated graphite surface. 29,30 Similar trends are observed for the S 2p spectra of graphite electrodes cycled with electrolyte containing added Me 3 NSO 3 and Et 3 NSO 3 . The S 2p peak intensity increases for the graphite electrodes cycled with either Me 3 NSO 3 or Et 3 NSO 3 as the additive concentration in the electrolyte increases ( Figure 5).…”

Section: Resultssupporting

confidence: 67%

Reversible Graphite Anode Cycling with PC-Based Electrolytes Enabled by Added Sulfur Trioxide Complexes

Demeaux

Dong

Lucht

2017

J. Electrochem. Soc.

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Pyridine sulfur trioxide (PyrSO 3 ), trimethyl amine sulfur trioxide (Me 3 NSO 3 ), and triethyl amine sulfur trioxide (Et 3 NSO 3 ) complexes have been investigated as electrolyte additives for lithium ion batteries. Incorporation of 0.5 to 2.0% of the SO 3 complexes into a PC/EMC (1:1 v/v) 1 M LiPF 6 baseline electrolyte affords reversible cycling of graphite anodes confirming generation of a stable Solid Electrolyte Interphase (SEI). Good cycling performance is observed for graphite/LiNi 0.5 Mn 1.5 O 4 cells cycled to high potential (4.8 V vs Li) containing PC based electrolyte with added SO 3 complexes. Ex-situ surface analysis via X-ray Photoelectron Spectroscopy (XPS) of the anodes reveals SO 3 complex reduction on the surface of the graphite anode generates a sulfur-based SEI containing sulfites, sulfide, and sulfate species. The presence of the sulfur containing species is likely critical for the stability of the SEI. Ex-situ XPS analyses of the LiNi 0.5 Mn 1.5 O 4 cathodes suggest that reaction of Me 3 NSO 3 or Et 3 NSO 3 complexes at high potential result in the generation of a stable passivation layer which affords good capacity retention and coulombic efficiency. The standard anode material in most commercial lithium ion batteries is graphite due to good specific capacity, low volumetric expansion upon Li + intercalation, relatively flat potential profile, excellent cyclability, and low cost. However, the reduction potential of lithiated graphite is below the stability window of most organic solvents and thus requires the formation of a Solid Electrolyte Interphase (SEI). 1,2Only a few electrolytes result in the formation of a stable SEI on graphite and most of these electrolytes include ethylene carbonate (EC) due to the critical role of EC in SEI formation.3 An alternative solvent, propylene carbonate (PC), has been already extensively studied for use in lithium-ion batteries due to its favorable physical properties: high relative permittivity (ε = 64.96) and wide operating temperature range (mp = -55• C, bp = 240 • C). 2 However, reduction of PC does not generate a stable SEI on graphite leading to continuous electrolyte reduction and graphite exfoliation. In addition, EC has recently been reported to have high reactivity with the surface of cathodes operating at high potential. 4,5 In order to use PC based electrolytes an electrolyte additive is required to assist with SEI formation. All of these sulfur compounds are soluble in the organic electrolytes, but anodic unstable at high potential. 6 Propane sultone is one of the most widely investigated sulfur based additives and has been reported to improve Li + conduction in the anode SEI. However, due to toxicity concerns there is an interest in finding an alternative to PS. Previously reported ex-situ surface analysis of graphite anodes cycled with PS suggests that the primary reduction product of PS is lithium propane sulfonate (RSO 3 Li). 19,20 In an effort to develop Additives for Designed Surface Modification (ADSM), 21 novel SO 3 based additiv...

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Section: Resultssupporting

confidence: 67%

Reversible Graphite Anode Cycling with PC-Based Electrolytes Enabled by Added Sulfur Trioxide Complexes

Demeaux

Dong

Lucht

2017

J. Electrochem. Soc.

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“…[40][41][42][43] As mall broadening of the main peak at higherb inding energy can be observed;t hus suggesting the presence of as mall amounto fC o 4 + .T hese results are in good agreement with the oxidation state of cobalt in the lithium analogues, namely,C o 3 + . When using internal energy calibration, it can be more relevant to rely on information provided by the overall peak structure, such as the satellitei ntensity and its positionr elative to the main peak.…”

Section: Resultssupporting

confidence: 67%

Passivation Layer and Cathodic Redox Reactions in Sodium‐Ion Batteries Probed by HAXPES

et al. 2015

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The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V).

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“…84,85 Also transition metal ion dissolution may be 86 An additional benefit may come in the form of lower first cycle irreversible capacity, since the coating restricts oxygen evolution and the subsequent irreversible transition metal migration to the Li + layer, ultimately leading to spinel formation. 84 MnO 2 coatings may take advantage of these phenomena, since formation of this material occurs at the surface of Li-rich materials during their electrochemical activation step anyways.…”

Section: Stabilization Of Voltage and Capacity Fadementioning

confidence: 99%

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

Erickson

Schipper

Penki

et al. 2017

J. Electrochem. Soc.

160

103

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Electrodes prepared from lithium-rich (Li-rich) xLi 2 MnO 3 ·(1-x)LiNi a Co b Mn c O 2 materials (a + b + c = 1) show extremely high discharge capacities, arising from excess Li + present in their Li 2 MnO 3 component, and the ability to reversibly store charge with O 2− anions. These electrodes suffer serious voltage and capacity fading however, due to the migration of transition metals to the Li-layer at advanced states of charging, partial structural layered-to-spinel transformation and other reasons. In this focus paper, the current understanding of the above materials is summarized, briefly concluding with attempts by our groups to mitigate the voltage and capacity fade of these electrodes.

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XPS Investigation of Surface Reactivity of Electrode Materials: Effect of the Transition Metal

Cited by 123 publications

References 33 publications

Reversible Graphite Anode Cycling with PC-Based Electrolytes Enabled by Added Sulfur Trioxide Complexes

Reversible Graphite Anode Cycling with PC-Based Electrolytes Enabled by Added Sulfur Trioxide Complexes

Passivation Layer and Cathodic Redox Reactions in Sodium‐Ion Batteries Probed by HAXPES

Review—Recent Advances and Remaining Challenges for Lithium Ion Battery Cathodes

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