Behavior of Cathode Materials at High Voltage

A special issue of Batteries (ISSN 2313-0105).

Deadline for manuscript submissions: closed (28 February 2024) | Viewed by 8609

Special Issue Editors

Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, IL 60439, USA
Interests: lithium-ion batteries; electrode/electrolyte interface

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Guest Editor
Department of Mechanical Engineering, The University of Arkansas, Fayetteville, AR 72701, USA
Interests: lithium-ion batteries; lithium metal batteries; battery interface engineering
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Special Issue Information

Dear Colleagues,

High-energy-density lithium-ion batteries are actively pursued for applications in electric vehicles to reduce our dependence on non-renewable fossil fuels. Among all cell components in LIBs, the cathodes that behave as the Li-supplying reservoir are currently the dominant factor limiting the energy density and cost. There is a clear trend to develop high-voltage cathodes for a better utilization of precious lithium reservoirs and to unlock their potential for a higher energy density.

In this Special Issue, we are seeking contributions helping to address the following:

  • Understand the behavior of cathode materials at a high voltage;
  • Understand the stability of the cathode–electrolyte interface;
  • Illustrate the failure mechanisms through advanced characterization;
  • Investigate the functionality of cathode materials and the cathode–electrolyte interface through multiscale modeling;
  • Develop mitigating solutions to improve the stability of the cathode materials and the cathode–electrolyte interface.

Dr. Zonghai Chen
Dr. Xiangbo Meng
Guest Editors

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Keywords

  • lithium-ion battery
  • cathode
  • cathode electrolyte interface
  • high voltage
  • surface modification
  • electrolyte

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Published Papers (3 papers)

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Research

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12 pages, 2378 KiB  
Article
Functional Surface Coating to Enhance the Stability of LiNi0.6Mn0.2Co0.2O2
by Yingying Xie, Matthew Li, Jiantao Li, Xiaozhou Huang, Jiyu Cai, Zhenzhen Yang, Hoai Nguyen, Baasit ali Shaik sulaiman, Niloofar Karami, Natalya A. Chernova, Shailesh Upreti, Brad Prevel, Feng Wang and Zonghai Chen
Batteries 2023, 9(10), 485; https://doi.org/10.3390/batteries9100485 - 23 Sep 2023
Cited by 1 | Viewed by 1940
Abstract
Parasitic reactions are responsible for continuous performance loss during the normal operation and storage of lithium-ion batteries, particularly for those using nickel-rich cathode materials. Among many contributors, residual Li2CO3 on the surface of nickel-rich cathodes plays a detrimental role in [...] Read more.
Parasitic reactions are responsible for continuous performance loss during the normal operation and storage of lithium-ion batteries, particularly for those using nickel-rich cathode materials. Among many contributors, residual Li2CO3 on the surface of nickel-rich cathodes plays a detrimental role in promoting parasitic reactions, and hence accelerates the performance loss of those cathode materials. In this work, a wet impregnation process was utilized to convert the detrimental Li2CO3 and LiOH impurities into a beneficial functional surface coating comprising phosphates. Specifically, hydro-phosphates were used as the functional surface modification agents to mitigate the detrimental effect of surface residuals. The best electrochemical performance was achieved by modifying LiNi0.6Mn0.2Co0.2O2 with a diluted dihydro-phosphate solution (pKa = 7.2), while the metal cation had a negligible impact on the electrochemical performance. This work provides a cheap and simple method for enabling the high performance of nickel-rich cathodes. Full article
(This article belongs to the Special Issue Behavior of Cathode Materials at High Voltage)
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16 pages, 8987 KiB  
Article
Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi0.5Mn1.5O4
by Bingning Wang, Seoung-Bum Son, Pavan Badami, Stephen E. Trask, Daniel Abraham, Yang Qin, Zhenzhen Yang, Xianyang Wu, Andrew Jansen and Chen Liao
Batteries 2023, 9(9), 435; https://doi.org/10.3390/batteries9090435 - 24 Aug 2023
Cited by 1 | Viewed by 2445
Abstract
In our initial study on the high-voltage 5 V cobalt-free spinel LiNi0.5Mn1.5O4 (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a [...] Read more.
In our initial study on the high-voltage 5 V cobalt-free spinel LiNi0.5Mn1.5O4 (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF6 in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm2) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as 1H NMR, 19F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions. Full article
(This article belongs to the Special Issue Behavior of Cathode Materials at High Voltage)
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Review

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20 pages, 7957 KiB  
Review
Understanding High-Voltage Behavior of Sodium-Ion Battery Cathode Materials Using Synchrotron X-ray and Neutron Techniques: A Review
by Vadim Shipitsyn, Rishivandhiga Jayakumar, Wenhua Zuo, Bing Sun and Lin Ma
Batteries 2023, 9(9), 461; https://doi.org/10.3390/batteries9090461 - 11 Sep 2023
Cited by 3 | Viewed by 3345
Abstract
Despite substantial research efforts in developing high-voltage sodium-ion batteries (SIBs) as high-energy-density alternatives to complement lithium-ion-based energy storage technologies, the lifetime of high-voltage SIBs is still associated with many fundamental scientific questions. In particular, the structure phase transition, oxygen loss, and cathode–electrolyte interphase [...] Read more.
Despite substantial research efforts in developing high-voltage sodium-ion batteries (SIBs) as high-energy-density alternatives to complement lithium-ion-based energy storage technologies, the lifetime of high-voltage SIBs is still associated with many fundamental scientific questions. In particular, the structure phase transition, oxygen loss, and cathode–electrolyte interphase (CEI) decay are intensely discussed in the field. Synchrotron X-ray and neutron scattering characterization techniques offer unique capabilities for investigating the complex structure and dynamics of high-voltage cathode behavior. In this review, to accelerate the development of stable high-voltage SIBs, we provide a comprehensive and thorough overview of the use of synchrotron X-ray and neutron scattering in studying SIB cathode materials with an emphasis on high-voltage layered transition metal oxide cathodes. We then discuss these characterizations in relation to polyanion-type cathodes, Prussian blue analogues, and organic cathode materials. Finally, future directions of these techniques in high-voltage SIB research are proposed, including CEI studies for polyanion-type cathodes and the extension of neutron scattering techniques, as well as the integration of morphology and phase characterizations. Full article
(This article belongs to the Special Issue Behavior of Cathode Materials at High Voltage)
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