Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles

doi:10.1039/c9ta01720h

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Title: Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles

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Abstract

The structural integrity of layered Ni-rich oxide cathode materials is one of the most significant factors that critically affect the performance and reliability of lithium-ion batteries. Prolonged battery operation many times involves repeated phase transitions, buildup of mechanical stresses, and could provoke thermal spikes. Such sophisticated chemo-thermo-mechanical interplay can cause performance degradation through structural disintegration of the cathode active materials (CAMs). In this work, we systematically investigate the thermal decomposition, fracture, and oxygen evolution of chemically delithiated Li _0.3Ni _0.8Co _0.15Al _0.05O ₂ (NCA) particles upon heating from 25 °C to 450 °C using a number of advanced X-ray and electron probes. We observed a continuous reduction of the Ni oxidation state upon heating, as well as the release of oxygen from the NCA lattice that undergoes the thermally induced phase transformations. The release of oxygen also created numerous mesopores throughout the analyzed particles, which could significantly affect the chemical and mechanical properties of the electrode. In addition, intergranular and intragranular fracturing at elevated temperatures also contribute to the degradation of the NCA cathode under these conditions. Our investigation of the mechanical integrity at elevated temperatures provides a fundamental understanding of the thermally driven chemomechanical breakdown of the NCA cathodemore » active materials.« less

Authors:

^[1];

^[2]; Wei, Chenxi ^[3];

^[4]; Alvarado, Judith ^[5]; Boell, Julian ^[4]; Nordlund, Dennis ^[3]; Schneider, Gerhard ^[6]; Hellstrom, Sondra ^[4]; Johnston, Christina ^[4];

^[4];

^[5];

^[3];

^[4]

Robert Bosch LLC, Sunnyvale, CA (United States); Karlsruhe Inst. of Technology (KIT) (Germany)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Robert Bosch LLC, Sunnyvale, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Karlsruhe Inst. of Technology (KIT) (Germany); Aalen Univ. (Germany)

Publication Date:: 2019-04-24

Research Org.:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1547284

Alternate Identifier(s):: OSTI ID: 1511062

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Materials Chemistry. A

Additional Journal Information:: Journal Volume: 7; Journal Issue: 20; Journal ID: ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Citation Formats


                    Besli, Münir M., Shukla, Alpesh Khushalchand, Wei, Chenxi, Metzger, Michael, Alvarado, Judith, Boell, Julian, Nordlund, Dennis, Schneider, Gerhard, Hellstrom, Sondra, Johnston, Christina, Christensen, Jake, Doeff, Marca M., Liu, Yijin, and Kuppan, Saravanan. Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles.  United States: N. p., 2019. 
        Web.  doi:10.1039/c9ta01720h.

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                    Besli, Münir M., Shukla, Alpesh Khushalchand, Wei, Chenxi, Metzger, Michael, Alvarado, Judith, Boell, Julian, Nordlund, Dennis, Schneider, Gerhard, Hellstrom, Sondra, Johnston, Christina, Christensen, Jake, Doeff, Marca M., Liu, Yijin, & Kuppan, Saravanan. Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles.  United States.  doi:10.1039/c9ta01720h.

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                    Besli, Münir M., Shukla, Alpesh Khushalchand, Wei, Chenxi, Metzger, Michael, Alvarado, Judith, Boell, Julian, Nordlund, Dennis, Schneider, Gerhard, Hellstrom, Sondra, Johnston, Christina, Christensen, Jake, Doeff, Marca M., Liu, Yijin, and Kuppan, Saravanan. Wed .  
        "Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles".  United States.  doi:10.1039/c9ta01720h.

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@article{osti_1547284,

  title        = {Thermally-driven mesopore formation and oxygen release in delithiated NCA cathode particles},

  author       = {Besli, Münir M. and Shukla, Alpesh Khushalchand and Wei, Chenxi and Metzger, Michael and Alvarado, Judith and Boell, Julian and Nordlund, Dennis and Schneider, Gerhard and Hellstrom, Sondra and Johnston, Christina and Christensen, Jake and Doeff, Marca M. and Liu, Yijin and Kuppan, Saravanan},

  abstractNote = {The structural integrity of layered Ni-rich oxide cathode materials is one of the most significant factors that critically affect the performance and reliability of lithium-ion batteries. Prolonged battery operation many times involves repeated phase transitions, buildup of mechanical stresses, and could provoke thermal spikes. Such sophisticated chemo-thermo-mechanical interplay can cause performance degradation through structural disintegration of the cathode active materials (CAMs). In this work, we systematically investigate the thermal decomposition, fracture, and oxygen evolution of chemically delithiated Li0.3Ni0.8Co0.15Al0.05O2 (NCA) particles upon heating from 25 °C to 450 °C using a number of advanced X-ray and electron probes. We observed a continuous reduction of the Ni oxidation state upon heating, as well as the release of oxygen from the NCA lattice that undergoes the thermally induced phase transformations. The release of oxygen also created numerous mesopores throughout the analyzed particles, which could significantly affect the chemical and mechanical properties of the electrode. In addition, intergranular and intragranular fracturing at elevated temperatures also contribute to the degradation of the NCA cathode under these conditions. Our investigation of the mechanical integrity at elevated temperatures provides a fundamental understanding of the thermally driven chemomechanical breakdown of the NCA cathode active materials.},

  doi          = {10.1039/c9ta01720h},

  journal      = {Journal of Materials Chemistry. A},

  number       = 20,

  volume       = 7,

  place        = {United States},

  year         = {2019},

  month        = {4}

}

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