Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

Dai, Kehua; Shao, Weiwei; Zhao, Beibei; Zhang, Wenjuan; Feng, Yan; Mao, Wenfeng; Ai, Guo; Liu, Gao; Mao, Jing; Yang, Wanli

doi:10.1016/j.jechem.2022.01.004

Cited by 5 publications

(4 citation statements)

References 50 publications

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“…Using the same TiMS method, a spinel LiMn 2 O 4 cathode shows irreversible q Mn of ˜0.1 mol e mol −1 after the first-discharge cutoff, (Figure S2a,d, Supporting Information) which agrees with other studies employing X-ray spectroscopy. [44] This experimental agreement on the spinel not only validates our TiMS method again, but also suggests different irreversible-capacity origins between DRX and ordered cathode materials (Figure 4a vs. Figure S2d, Supporting Information).…”

Section: First-cycle Redox Componentssupporting

confidence: 76%

“…Figure S2d, Supporting Information). In other words, discharged ordered materials have residual oxidized TM left from incomplete lithiation, [44,45] which governs their first-cycle irreversible capacities. On the other hand, disordered LMTO's irreversible capacity is dominated by parasitic components (q side ≈ 0.11 mol e mol −1 ), which implies that engineering the DRX-electrolyte interface promises to achieve a higher overall coulombic efficiency CE.…”

Section: First-cycle Redox Componentsmentioning

confidence: 99%

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Quantitative Decoupling of Oxygen‐Redox and Manganese‐Redox Voltage Hysteresis in a Cation‐Disordered Rock Salt Cathode

Huang

Cai

Crafton

et al. 2023

Advanced Energy Materials

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Pronounced voltage hysteresis in Li-excess cathode materials is commonly thought to be associated with oxygen redox. However, these materials often possess overlapping oxygen and transition-metal redox, whose contributions to hysteresis between charge and discharge are challenging to distinguish. In this work, a two-step aqueous redox titration is developed with the aid of mass spectrometry (MS) to quantify oxidized lattice oxygen and Mn 3+ /4+ redox in a representative Li-excess cation-disordered rock salt-Li 1.2 Mn 0.4 Ti 0.4 O 2 (LMTO). Two MS-countable gas molecules evolve from two separate titrant-analyte reactions, thereby allowing Mn and O redox capacities to be decoupled. The decoupled O and Mn redox coulombic efficiencies are close to 100% for the LMTO cathode, indicating high charge-compensation reversibility. As incremental Mn and O redox capacities are quantitatively decoupled, each redox voltage hysteresis is further evaluated. Overall, LMTO voltage hysteresis arises not only from an intrinsic charge-discharge voltage mismatch related to O redox, but also from asymmetric Mn-redox overvoltages. The results reveal that O and Mn redox both contribute substantially to voltage hysteresis. This work further shows the potential of designing new analytical workflows to experimentally quantify key properties, even in a disordered material having complex local coordination environments.

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Section: First-cycle Redox Componentssupporting

confidence: 76%

Section: First-cycle Redox Componentsmentioning

confidence: 99%

Quantitative Decoupling of Oxygen‐Redox and Manganese‐Redox Voltage Hysteresis in a Cation‐Disordered Rock Salt Cathode

Huang

Cai

Crafton

et al. 2023

Advanced Energy Materials

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“…This is considered one of the main reasons for capacity fading in LMO. 63 Dai et al 64 prepared a series of LMO electrodes with different charge/discharge states and revealed that Mn 2+ is easily generated at the surface of the material, as shown in Figs. 5a -5d.…”

Section: Degradation Mechanisms Of Spinel Limn 2 Omentioning

confidence: 99%

Research Development on Spinel Lithium Manganese Oxides Cathode Materials for Lithium-Ion Batteries

Zhang,

Zhou

et al. 2023

J. Electrochem. Soc.

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Spinel LiMn2O4 (LMO) is a cathode material that features 3D Li+ diffusion channels, and it offers a range of benefits including low cost, non-toxicity, environmental friendliness, high safety, and excellent rate performance. Consequently, it has become a popular cathode material for lithium-ion batteries, having gained practical application. However, the cycling performance of LMO is still limited by problems such as Jahn-Teller distortion and Mn dissolution. In recent years, researchers have proposed various preparation and modification methods to address these problems and achieve wider commercialization of LMO cathode materials. This paper introduces the spinel structure of LMO and its degradation mechanisms, listing several common methods for synthesizing LMO cathode materials and modification approaches aimed at improving cyclic stability.

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“…Additionally, the bulk evolution is consistent with the red-shift of the Mn L 3 -edge in iPFY mode (Figure S10). 58 The evolution of the electronic state of Ru has been studied by Ru 3p XPS as depicted in Figure 4a. Due to the spin− orbital coupling effect, the peaks at about 464.2 and 486.3 eV are attributed to the Ru 3p 3/2 and 3p 1/2 features, respectively.…”

mentioning

confidence: 99%

The Effect of Key Electronic States on Excess Lithium Intercalation in Li₂Ru_yMn_1–yO₃

Zheng

et al. 2023

J. Phys. Chem. Lett.

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Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

Cited by 5 publications

References 50 publications

Quantitative Decoupling of Oxygen‐Redox and Manganese‐Redox Voltage Hysteresis in a Cation‐Disordered Rock Salt Cathode

Quantitative Decoupling of Oxygen‐Redox and Manganese‐Redox Voltage Hysteresis in a Cation‐Disordered Rock Salt Cathode

Research Development on Spinel Lithium Manganese Oxides Cathode Materials for Lithium-Ion Batteries

The Effect of Key Electronic States on Excess Lithium Intercalation in Li₂Ru_yMn_1–yO₃

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Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

Cited by 5 publications

References 50 publications

Quantitative Decoupling of Oxygen‐Redox and Manganese‐Redox Voltage Hysteresis in a Cation‐Disordered Rock Salt Cathode

Quantitative Decoupling of Oxygen‐Redox and Manganese‐Redox Voltage Hysteresis in a Cation‐Disordered Rock Salt Cathode

Research Development on Spinel Lithium Manganese Oxides Cathode Materials for Lithium-Ion Batteries

The Effect of Key Electronic States on Excess Lithium Intercalation in Li2RuyMn1–yO3

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The Effect of Key Electronic States on Excess Lithium Intercalation in Li₂Ru_yMn_1–yO₃