Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li7La3Zr2O12

Kun, Robert; Langer, Frederieke; Delle Piane, Massimo; Ohno, Saneyuki; Zeier, Wolfgang G.; Gockeln, Michael; Colombi Ciacchi, Lucio; Busse, Matthias; Fekete, István

doi:10.1021/acsami.8b09789

Title: Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li₇La₃Zr₂O₁₂

Abstract

Li₇La₃Zr₂O₁₂ (LLZO) and related compounds are considered as promising candidates for future all-solid-state Li-ion battery applications. Still, the processing of those materials into thin membranes with the right stoichiometry and crystal structure is difficult and laborious. The sensitivity of the Li-ion conductive garnets against moisture and the associated Li⁺/H⁺ cation exchange makes their processing even more difficult. Formulation of suitable polymer/ceramic hybrid solid state electrolytes could be a prosperous way to reach the future large scale production of solid state Li-ion batteries. In fact, solvent mediated and/or slurry based wet-processing of the LLZO, e.g., tape-casting, could result in irreversible Li-ion loss of the pristine material due to Li⁺/H⁺ cation exchange. The concomitant structural changes and loss in functionality in terms of Li-ion conductivity are the results of the above process. As such, in the present work a systematic study on the chemical stability and structural retention of Al-substituted LLZO in different solvents is reported. It was found that Li⁺/H⁺ exchange in LLZO occurs upon solvent immersion, and its magnitude is dependent on the availability of –OH functional groups of the solvent molecules. As a result, a larger degree of Li⁺/H⁺ exchange causes higher increase of the lattice parameter of themore »« less

Authors:

^[1]; Langer, Frederieke ^[2];

^[3];

^[4];

^[4]; Gockeln, Michael ^[3];

^[3]; Busse, Matthias ^[5]; Fekete, István ^[6]

Univ. of Bremen (Germany); Fraunhofer Inst. for Manufacturing Technology and Advanced Materials (IFAM), Bremen (Germany)
Fraunhofer Inst. for Manufacturing Technology and Advanced Materials (IFAM), Bremen (Germany)
Univ. of Bremen (Germany)
Justus-Liebig-Univ., Giessen (Germany)
Fraunhofer Inst. for Manufacturing Technology and Advanced Materials (IFAM), Bremen (Germany); Univ. of Bremen (Germany)
Univ. of Szeged (Hungary)

Publication Date:: Mon Oct 08 00:00:00 EDT 2018

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Org.:: German Excellence Initiative; USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1483095

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 10; Journal Issue: 43; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: ENGLISH

Subject:: 36 MATERIALS SCIENCE; garnet type Li7La3Zr2O12; lithium ion conductor; solvent compatibility; wet-processing; composite electrolyte; all-solid-state Li-ion battery

Citation Formats


                    Kun, Robert, Langer, Frederieke, Delle Piane, Massimo, Ohno, Saneyuki, Zeier, Wolfgang G., Gockeln, Michael, Colombi Ciacchi, Lucio, Busse, Matthias, and Fekete, István. Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li7La3Zr2O12.  United States: N. p., 2018. 
Web.  doi:10.1021/acsami.8b09789.

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                    Kun, Robert, Langer, Frederieke, Delle Piane, Massimo, Ohno, Saneyuki, Zeier, Wolfgang G., Gockeln, Michael, Colombi Ciacchi, Lucio, Busse, Matthias, & Fekete, István. Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li7La3Zr2O12.  United States.  https://doi.org/10.1021/acsami.8b09789

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                    Kun, Robert, Langer, Frederieke, Delle Piane, Massimo, Ohno, Saneyuki, Zeier, Wolfgang G., Gockeln, Michael, Colombi Ciacchi, Lucio, Busse, Matthias, and Fekete, István. Mon .  
"Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li7La3Zr2O12".  United States.  https://doi.org/10.1021/acsami.8b09789.  https://www.osti.gov/servlets/purl/1483095.

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@article{osti_1483095,

  title        = {Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li7La3Zr2O12},

  author       = {Kun, Robert and Langer, Frederieke and Delle Piane, Massimo and Ohno, Saneyuki and Zeier, Wolfgang G. and Gockeln, Michael and Colombi Ciacchi, Lucio and Busse, Matthias and Fekete, István},

  abstractNote = {Li7La3Zr2O12 (LLZO) and related compounds are considered as promising candidates for future all-solid-state Li-ion battery applications. Still, the processing of those materials into thin membranes with the right stoichiometry and crystal structure is difficult and laborious. The sensitivity of the Li-ion conductive garnets against moisture and the associated Li+/H+ cation exchange makes their processing even more difficult. Formulation of suitable polymer/ceramic hybrid solid state electrolytes could be a prosperous way to reach the future large scale production of solid state Li-ion batteries. In fact, solvent mediated and/or slurry based wet-processing of the LLZO, e.g., tape-casting, could result in irreversible Li-ion loss of the pristine material due to Li+/H+ cation exchange. The concomitant structural changes and loss in functionality in terms of Li-ion conductivity are the results of the above process. As such, in the present work a systematic study on the chemical stability and structural retention of Al-substituted LLZO in different solvents is reported. It was found that Li+/H+ exchange in LLZO occurs upon solvent immersion, and its magnitude is dependent on the availability of –OH functional groups of the solvent molecules. As a result, a larger degree of Li+/H+ exchange causes higher increase of the lattice parameter of the LLZO, determined by synchrotron diffraction analyses. The expansion of the cubic unit cell was ascertained, when Li+ was replaced by H+ in the host lattice, by ab initio computational studies. The application of the most common solvent as dispersion medium, i.e., high purity water, causes the most significant Li+/H+ exchange and, therefore, structural change, while acetonitrile was proven to be the best suitable solvent for wet postprocessing of LLZO. Finally, computational calculations suggested that the Li+/H+ exchange could result in diminished ionic, i.e., mixed Li+–H+, conductivity due to the insertion of protons with lower mobility than that of Li-ions.},

  doi          = {10.1021/acsami.8b09789},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 43,

  volume       = 10,

  place        = {United States},

  year         = {Mon Oct 08 00:00:00 EDT 2018},

  month        = {Mon Oct 08 00:00:00 EDT 2018}

}

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https://doi.org/10.1021/acsami.8b09789

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Cited by: 22 works

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Figures / Tables:

Figure 1: Representative Rietveld refinement for the pristine LLZO, including profile fit and profile difference using three LLZO phases and the impurity phase Li₂ZrO₃. The top ticks are for the majority LLZO (LLZO1) phase and the bottom ones are for the La-deficient minor impurity Li₂ZrO₃. The inset is showing amore »

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Title: Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li7La3Zr2O12

Abstract

Citation Formats

Figures / Tables:

Title: Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li₇La₃Zr₂O₁₂