Manganese in the SEI Layer of Li4Ti5O12 Studied by Combined NEXAFS and HAXPES Techniques

Nordh, Tim; Younesi, Reza; Hahlin, Maria; Duarte, Roberto Félix; Tengstedt, Carl; Brandell, Daniel; Edström, Kristina

doi:10.1021/acs.jpcc.5b11756

Cited by 48 publications

(46 citation statements)

References 30 publications

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“…However, according to a series comparison tests, Wu et al [14] found that moisture contributes less to cell swelling. With the aid of hard X-ray photoelectron spectroscopy (HAXPES) and nearedge X-ray absorption fine structure (NEXAFS), Nordh et al [148] found that an SEI film was formed on the Li 4 Ti 5 O 12 electrode. They found that the cells with a certain amount of (15 of 25) 1601625 wileyonlinelibrary.com DMC solvent having much more D 2 O in the electrolyte showed no observable D 2 and minimal H-D signals, indicating that the hydrogen gas was generated by the co-reduction of DMC and water.…”

Section: Reasons For Gas Formationmentioning

confidence: 99%

“…However, in the recent years, more and more researchers have argued that an SEI film could form on the surface of Li 4 Ti 5 O 12 anode even above 1 V, and higher temperatures could accelerate the surface formation of the so-called SEI film. [148] He et al [12] proposed that anatase TiO 2 can also form at the very thin outermost surface of the Li 4 Ti 5 O 12 (111) plane, which results in a transformation from the (111) to the (222) plane of Li 4 Ti 5 O 12 and the formation of the (101) plane of TiO 2 according to the reaction equation in Scheme 1b. They determined that Li 2 CO 3 , LiF, and ROCO 2 Li mainly formed on the Li 4 Ti 5 O 12 surface, which agrees with the reactions in Scheme 1.…”

Section: Interface Chemistrymentioning

confidence: 99%

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Challenges of Spinel Li₄Ti₅O₁₂ for Lithium‐Ion Battery Industrial Applications

Yuan

Tan

et al. 2017

Advanced Energy Materials

347

233

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Section: Reasons For Gas Formationmentioning

confidence: 99%

Section: Interface Chemistrymentioning

confidence: 99%

Challenges of Spinel Li₄Ti₅O₁₂ for Lithium‐Ion Battery Industrial Applications

Yuan

Tan

et al. 2017

Advanced Energy Materials

347

233

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“…26 The differences in electrochemical behavior can then more easily be attributed to the modifications on the positive electrode. Even though LTO electrodes generate some electrolyte reduction, 27,28 this cell chemistry can still be considered a good base system to study the effect of electrolyte additives on the cathode side.…”

mentioning

confidence: 99%

The Effect of the Fluoroethylene Carbonate Additive in LiNi_0.5Mn_1.5O₄- Li₄Ti₅O₁₂Lithium-Ion Cells

Aktekin

Younesi

Zipprich³

et al. 2017

J. Electrochem. Soc.

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The effect of the electrolyte additive fluoroethylene carbonate (FEC) for Li-ion batteries has been widely discussed in literature in recent years. Here, the additive is studied for the high-voltage cathode LiNi 0.5 Mn 1.5 O 4 (LNMO) coupled to Li 4 Ti 5 O 12 (LTO) to specifically study its effect on the cathode side. Electrochemical performance of full cells prepared by using a standard electrolyte (LP40) with different concentrations of FEC (0, 1 and 5 wt%) were compared and the surface of cycled positive electrodes were analyzed by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The results show that addition of FEC is generally of limited use for this battery system. Addition of 5 wt% FEC results in relatively poor cycling performance, while the cells with 1 wt% FEC showed similar behavior compared to reference cells prepared without FEC. SEM and XPS analysis did not indicate the formation of thick surface layers on the LNMO cathode, however, an increase in layer thickness with increased FEC content in the electrolyte could be observed. XPS analysis on LTO electrodes showed that the electrode interactions between positive and negative electrodes occurred as Mn and Ni were detected on the surface of LTO already after 1 cycle. 1 In addition to the high voltage plateau, the intrinsic structure of the spinel phase allows fast lithiation and de-lithiation kinetics 2,3 which is attributed to the 3-D lithium transport among the available tunnels in the crystal. 4 The advantage of higher voltage (thus higher energy density) and good power capability are two main reasons behind the growing interest for this material, especially for electric vehicle applications. However, the electrode material is prone to side reactions with conventional electrolytes, not least electrolyte decomposition at high voltages and transition metal dissolution from the spinel structure, particularly observed at elevated temperatures. These obstacles need to be resolved before wide-scale commercial application of LNMO electrodes. 5,6 One possible approach to overcome these problems is to use electrolyte additives that could ideally form an in-situ passivating layer on the positive electrode surface, similarly to the solid electrolyte interphase (SEI) observed on negative LiB electrodes. 7,8 A number of electrolyte additives have been reported in recent years for the purpose of passivating the cathode/electrolyte interface at high operating voltages.7 Some of these additives include LiBOB, 9 succinic anhydride, 10 HFiP 11 and DMMP. 12 It is important to note that the use of such cathode interface additives should also be compatible with the anode interface in full cells, or vice versa for additives intended for the anode side. Therefore, it is essential to study the effect of anode additives on the cathode side as well, if new fullcell chemistries are to be realized. Fluoroethylene carbonate (FEC) and vinylene carbonate (VC) are common examples of such additives where the former has been used mostly to improve an...

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“…The P 2p spectra show a peak at 135.5 eV, primarily corresponding to the salt anion . The spectrum of the electrode cycled at −10 °C has a higher intensity contribution at 138 eV and smaller at 135 eV, where the contribution at 138 eV likely comes from a different degradation product of the LiPF 6 salt.…”

Section: Resultsmentioning

confidence: 96%

“…Despite the formation of a surface layer on LTO, it is to a smaller extent than that observed for other negative electrode materials such as graphite or a lithium foil . The surface layer on LTO does not necessarily consist of only degraded electrolyte species; also, manganese can be deposited on the surface when LTO has been cycled against LiMn 2 O 4 . Recently, Aktekin et al showed how electrolyte reduction on LTO can limit the capacity of cells .…”

Section: Introductionmentioning

confidence: 99%

Temperature Dependence of Electrochemical Degradation in LiNi_1/3Mn_1/3Co_1/3O₂/Li₄Ti₅O₁₂ Cells

et al. 2019

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Aging mechanisms in lithium‐ion batteries are dependent on the operational temperature, but the detailed mechanisms on what processes take place at what temperatures are still lacking. The electrochemical performance and capacity fading of the common cell chemistry LiNi1/3Mn1/3Co1/3O2 (NMC)/Li4Ti5O12 (LTO) pouch cells are studied at temperatures 10, 30, and 55 °C. The full cells are cycled with a moderate upper cutoff potential of 4.3 V versus Li+/Li. The electrode interfaces are characterized postmortem using photoelectron spectroscopy techniques (soft X‐ray photoelectron spectroscopy [SOXPES], hard X‐ray photoelectron spectroscopy [HAXPES], and X‐ray absorption near edge structure [XANES]). Stable cycling at 30 °C is explained by electrolyte reduction forming a stabilizing interphase, thereby preventing further degradation. This initial reaction, between LTO and the electrolyte, seems to be beneficial for the NMC–LTO full cell. At 55 °C, continuous electrolyte reduction and capacity fading are observed. It leads to the formation of a thicker surface layer of organic species on the LTO surface than at 30 °C, contributing to an increased voltage hysteresis. At 10 °C, large cell‐resistances are observed, caused by poor electrolyte conductivity in combination with a relatively thicker and LixPFy‐rich surface layer on LTO, which limit the capacity.

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Manganese in the SEI Layer of Li₄Ti₅O₁₂ Studied by Combined NEXAFS and HAXPES Techniques

Cited by 48 publications

References 30 publications

Challenges of Spinel Li₄Ti₅O₁₂ for Lithium‐Ion Battery Industrial Applications

Challenges of Spinel Li₄Ti₅O₁₂ for Lithium‐Ion Battery Industrial Applications

The Effect of the Fluoroethylene Carbonate Additive in LiNi_0.5Mn_1.5O₄- Li₄Ti₅O₁₂Lithium-Ion Cells

Temperature Dependence of Electrochemical Degradation in LiNi_1/3Mn_1/3Co_1/3O₂/Li₄Ti₅O₁₂ Cells

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Manganese in the SEI Layer of Li4Ti5O12 Studied by Combined NEXAFS and HAXPES Techniques

Cited by 48 publications

References 30 publications

Challenges of Spinel Li4Ti5O12 for Lithium‐Ion Battery Industrial Applications

Challenges of Spinel Li4Ti5O12 for Lithium‐Ion Battery Industrial Applications

The Effect of the Fluoroethylene Carbonate Additive in LiNi0.5Mn1.5O4- Li4Ti5O12Lithium-Ion Cells

Temperature Dependence of Electrochemical Degradation in LiNi1/3Mn1/3Co1/3O2/Li4Ti5O12 Cells

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Manganese in the SEI Layer of Li₄Ti₅O₁₂ Studied by Combined NEXAFS and HAXPES Techniques

Challenges of Spinel Li₄Ti₅O₁₂ for Lithium‐Ion Battery Industrial Applications

Challenges of Spinel Li₄Ti₅O₁₂ for Lithium‐Ion Battery Industrial Applications

The Effect of the Fluoroethylene Carbonate Additive in LiNi_0.5Mn_1.5O₄- Li₄Ti₅O₁₂Lithium-Ion Cells

Temperature Dependence of Electrochemical Degradation in LiNi_1/3Mn_1/3Co_1/3O₂/Li₄Ti₅O₁₂ Cells