Toward Stable, High-Energy, Partially Disordered Mn-Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation

Dawei Xia; Junyi Yao; Chenguang Shi; Qian Wang; Changgyu Seok; Afolabi Olayiwola; Weibo Huang; Dennis Nordlund; Si Athena Chen; Cheng Jun Sun; Luxi Li; Dewen Hou; Lina Quan; Yuzi Liu; Hui Xiong; Feng Lin

doi:10.1002/adma.202501352

Toward Stable, High-Energy, Partially Disordered Mn-Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation

Dawei Xia
, Junyi Yao
, Chenguang Shi
, Qian Wang
, Changgyu Seok
, Afolabi Olayiwola
, Weibo Huang
, Dennis Nordlund
, Si Athena Chen
, Cheng Jun Sun
, Luxi Li
, Dewen Hou
, Lina Quan
, Yuzi Liu
, Hui Xiong
, Feng Lin

Powder Diffraction

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Mn-rich cathodes balance performance and sustainability but suffer from limited cyclability due to Mn dissolution and cathode-to-anode crosstalk. The Jahn-Teller (J-T) effect of Mn³⁺ is often linked to the above phenomena, such as in spinel LiMn₂O₄. However, in typical voltage ranges, significant Mn³⁺ only appears near the end of discharge, highlighting the need to reassess its role in driving Mn dissolution, structural degradation, and battery performance. Here, the spinel cathode's degree of disorder is tailored to expand the Mn redox range, enabling segmentation into J-T active and less active voltage ranges. Cycling at segmented voltage windows reveals surface degradation mechanisms with and without the major J-T effect. Despite a stronger J-T effect below 3.6 V vs. Li/Li⁺, Mn dissolution is less significant than above 3.6 V. Expanding the cycling window to 2.0–4.3 V causes severe degradation as the J-T active range induces a tetragonal phase and Mn²⁺-rich surface, driving Mn dissolution and consuming Li-ion inventory in full cells. Reducing electrolyte acidity minimizes Mn³⁺ disproportionation, enabling a stable dopant-free Mn-only cathode with a 250 mAh g⁻¹ specific capacity. These findings demonstrate that full cells using Mn-rich cathodes have the potential to avoid the notorious crosstalk problem through electrolyte engineering.

Original language	English
Article number	2501352
Journal	Advanced Materials
Volume	37
Issue number	34
DOIs	https://doi.org/10.1002/adma.202501352
State	Published - Aug 28 2025

Funding

The work was supported by the National Science Foundation (DMR-2045570). This work used shared facilities at the Nanoscale Characterization and Fabrication Laboratory (NCFL), which is funded and managed by Virginia Tech's Institute for Critical Technology and Applied Science. Additional support is provided by the Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), a member of the National Nanotechnology Coordinated Infrastructure (NNCI), supported by NSF (ECCS 1542100 and ECCS 2025151). F.L. acknowledges the NCFL Faculty Fellowship program. D.X. and F.L. thank Dr. Hongyu Wang at NCFL, Virginia Tech for helping with TEM measurements. This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357. The use of the Stanford Synchrotron Radiation Lightsource (SSRL), SLAC National Accelerator Laboratory, was supported by the US DOE, Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02-76SF00515. A portion of this research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to HB-2C WAND2 on proposal number IPTS-32663.1. The work was supported by the National Science Foundation (DMR‐2045570). This work used shared facilities at the Nanoscale Characterization and Fabrication Laboratory (NCFL), which is funded and managed by Virginia Tech's Institute for Critical Technology and Applied Science. Additional support is provided by the Virginia Tech National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), a member of the National Nanotechnology Coordinated Infrastructure (NNCI), supported by NSF (ECCS 1542100 and ECCS 2025151). F.L. acknowledges the NCFL Faculty Fellowship program. D.X. and F.L. thank Dr. Hongyu Wang at NCFL, Virginia Tech for helping with TEM measurements. This research used resources of the Advanced Photon Source and Center for Nanoscale Materials, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the U.S. DOE under Contract No. DE‐AC02‐06CH11357. The use of the Stanford Synchrotron Radiation Lightsource (SSRL), SLAC National Accelerator Laboratory, was supported by the US DOE, Office of Science, Office of Basic Energy Sciences, under contract no. DE‐AC02‐76SF00515. A portion of this research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to HB‐2C WAND on proposal number IPTS‐32663.1.

Keywords

Mn dissolution
Mn-based electrodes
cation disorder
high-energy Li-ion batteries
spinel cathode

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10.1002/adma.202501352

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Xia, D., Yao, J., Shi, C., Wang, Q., Seok, C., Olayiwola, A., Huang, W., Nordlund, D., Chen, S. A., Sun, C. J., Li, L., Hou, D., Quan, L., Liu, Y., Xiong, H., & Lin, F. (2025). Toward Stable, High-Energy, Partially Disordered Mn-Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation. Advanced Materials, 37(34), Article 2501352. https://doi.org/10.1002/adma.202501352

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title = "Toward Stable, High-Energy, Partially Disordered Mn-Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation",

abstract = "Mn-rich cathodes balance performance and sustainability but suffer from limited cyclability due to Mn dissolution and cathode-to-anode crosstalk. The Jahn-Teller (J-T) effect of Mn3+ is often linked to the above phenomena, such as in spinel LiMn2O4. However, in typical voltage ranges, significant Mn3+ only appears near the end of discharge, highlighting the need to reassess its role in driving Mn dissolution, structural degradation, and battery performance. Here, the spinel cathode's degree of disorder is tailored to expand the Mn redox range, enabling segmentation into J-T active and less active voltage ranges. Cycling at segmented voltage windows reveals surface degradation mechanisms with and without the major J-T effect. Despite a stronger J-T effect below 3.6 V vs. Li/Li+, Mn dissolution is less significant than above 3.6 V. Expanding the cycling window to 2.0–4.3 V causes severe degradation as the J-T active range induces a tetragonal phase and Mn2+-rich surface, driving Mn dissolution and consuming Li-ion inventory in full cells. Reducing electrolyte acidity minimizes Mn3+ disproportionation, enabling a stable dopant-free Mn-only cathode with a 250 mAh g−1 specific capacity. These findings demonstrate that full cells using Mn-rich cathodes have the potential to avoid the notorious crosstalk problem through electrolyte engineering.",

keywords = "Mn dissolution, Mn-based electrodes, cation disorder, high-energy Li-ion batteries, spinel cathode",

author = "Dawei Xia and Junyi Yao and Chenguang Shi and Qian Wang and Changgyu Seok and Afolabi Olayiwola and Weibo Huang and Dennis Nordlund and Chen, \{Si Athena\} and Sun, \{Cheng Jun\} and Luxi Li and Dewen Hou and Lina Quan and Yuzi Liu and Hui Xiong and Feng Lin",

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T1 - Toward Stable, High-Energy, Partially Disordered Mn-Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation

AU - Xia, Dawei

AU - Yao, Junyi

AU - Shi, Chenguang

AU - Wang, Qian

AU - Seok, Changgyu

AU - Olayiwola, Afolabi

AU - Huang, Weibo

AU - Nordlund, Dennis

AU - Chen, Si Athena

AU - Sun, Cheng Jun

AU - Li, Luxi

AU - Hou, Dewen

AU - Quan, Lina

AU - Liu, Yuzi

AU - Xiong, Hui

AU - Lin, Feng

PY - 2025/8/28

Y1 - 2025/8/28

N2 - Mn-rich cathodes balance performance and sustainability but suffer from limited cyclability due to Mn dissolution and cathode-to-anode crosstalk. The Jahn-Teller (J-T) effect of Mn3+ is often linked to the above phenomena, such as in spinel LiMn2O4. However, in typical voltage ranges, significant Mn3+ only appears near the end of discharge, highlighting the need to reassess its role in driving Mn dissolution, structural degradation, and battery performance. Here, the spinel cathode's degree of disorder is tailored to expand the Mn redox range, enabling segmentation into J-T active and less active voltage ranges. Cycling at segmented voltage windows reveals surface degradation mechanisms with and without the major J-T effect. Despite a stronger J-T effect below 3.6 V vs. Li/Li+, Mn dissolution is less significant than above 3.6 V. Expanding the cycling window to 2.0–4.3 V causes severe degradation as the J-T active range induces a tetragonal phase and Mn2+-rich surface, driving Mn dissolution and consuming Li-ion inventory in full cells. Reducing electrolyte acidity minimizes Mn3+ disproportionation, enabling a stable dopant-free Mn-only cathode with a 250 mAh g−1 specific capacity. These findings demonstrate that full cells using Mn-rich cathodes have the potential to avoid the notorious crosstalk problem through electrolyte engineering.

AB - Mn-rich cathodes balance performance and sustainability but suffer from limited cyclability due to Mn dissolution and cathode-to-anode crosstalk. The Jahn-Teller (J-T) effect of Mn3+ is often linked to the above phenomena, such as in spinel LiMn2O4. However, in typical voltage ranges, significant Mn3+ only appears near the end of discharge, highlighting the need to reassess its role in driving Mn dissolution, structural degradation, and battery performance. Here, the spinel cathode's degree of disorder is tailored to expand the Mn redox range, enabling segmentation into J-T active and less active voltage ranges. Cycling at segmented voltage windows reveals surface degradation mechanisms with and without the major J-T effect. Despite a stronger J-T effect below 3.6 V vs. Li/Li+, Mn dissolution is less significant than above 3.6 V. Expanding the cycling window to 2.0–4.3 V causes severe degradation as the J-T active range induces a tetragonal phase and Mn2+-rich surface, driving Mn dissolution and consuming Li-ion inventory in full cells. Reducing electrolyte acidity minimizes Mn3+ disproportionation, enabling a stable dopant-free Mn-only cathode with a 250 mAh g−1 specific capacity. These findings demonstrate that full cells using Mn-rich cathodes have the potential to avoid the notorious crosstalk problem through electrolyte engineering.

KW - Mn dissolution

KW - Mn-based electrodes

KW - cation disorder

KW - high-energy Li-ion batteries

KW - spinel cathode

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SN - 0935-9648

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M1 - 2501352

ER -

Toward Stable, High-Energy, Partially Disordered Mn-Rich Spinel Cathodes by Revealing and Mitigating Surface Degradation

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Keywords

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