Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction
Among lithium battery cathode materials, Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> (LR-NMC) has a high theoretical capacity, but suffers from voltage and capacity fade during cycling. This is partially...
| Main Authors: | , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-10-01
|
| Series: | Symmetry |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-8994/13/11/1989 |
| _version_ | 1797508399400747008 |
|---|---|
| author | Matthias Quintelier Tyché Perkisas Romy Poppe Maria Batuk Mylene Hendrickx Joke Hadermann |
| author_facet | Matthias Quintelier Tyché Perkisas Romy Poppe Maria Batuk Mylene Hendrickx Joke Hadermann |
| author_sort | Matthias Quintelier |
| collection | DOAJ |
| description | Among lithium battery cathode materials, Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> (LR-NMC) has a high theoretical capacity, but suffers from voltage and capacity fade during cycling. This is partially ascribed to transition metal cation migration, which involves the local transformation of the honeycomb layered structure to spinel-like nano-domains. Determination of the honeycomb layered/spinel phase ratio from powder X-ray diffraction data is hindered by the nanoscale of the functional material and the domains, diverse types of twinning, stacking faults, and the possible presence of the rock salt phase. Determining the phase ratio from transmission electron microscopy imaging can only be done for thin regions near the surfaces of the crystals, and the intense beam that is needed for imaging induces the same transformation to spinel as cycling does. In this article, it is demonstrated that the low electron dose sufficient for electron diffraction allows the collection of data without inducing a phase transformation. Using calculated electron diffraction patterns, we demonstrate that it is possible to determine the volume ratio of the different phases in the particles using a pair-wise comparison of the intensities of the reflections. Using this method, the volume ratio of spinel structure to honeycomb layered structure is determined for a submicron sized crystal from experimental three-dimensional electron diffraction (3D ED) and precession electron diffraction (PED) data. Both twinning and the possible presence of the rock salt phase are taken into account. After 150 charge–discharge cycles, 4% of the volume in LR-NMC particles was transformed irreversibly from the honeycomb layered structure to the spinel structure. The proposed method would be applicable to other multi-phase materials as well. |
| first_indexed | 2024-03-10T05:02:29Z |
| format | Article |
| id | doaj.art-d6053cd5d0134d67a13578782a072275 |
| institution | Directory Open Access Journal |
| issn | 2073-8994 |
| language | English |
| last_indexed | 2024-03-10T05:02:29Z |
| publishDate | 2021-10-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Symmetry |
| spelling | doaj.art-d6053cd5d0134d67a13578782a0722752023-11-23T01:42:58ZengMDPI AGSymmetry2073-89942021-10-011311198910.3390/sym13111989Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron DiffractionMatthias Quintelier0Tyché Perkisas1Romy Poppe2Maria Batuk3Mylene Hendrickx4Joke Hadermann5EMAT, Department of Physics, University of Antwerp, 2020 Antwerp, BelgiumDepartment of Engineering Management, Faculty of Business and Economics, University of Antwerp, 2000 Antwerp, BelgiumEMAT, Department of Physics, University of Antwerp, 2020 Antwerp, BelgiumEMAT, Department of Physics, University of Antwerp, 2020 Antwerp, BelgiumEMAT, Department of Physics, University of Antwerp, 2020 Antwerp, BelgiumEMAT, Department of Physics, University of Antwerp, 2020 Antwerp, BelgiumAmong lithium battery cathode materials, Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> (LR-NMC) has a high theoretical capacity, but suffers from voltage and capacity fade during cycling. This is partially ascribed to transition metal cation migration, which involves the local transformation of the honeycomb layered structure to spinel-like nano-domains. Determination of the honeycomb layered/spinel phase ratio from powder X-ray diffraction data is hindered by the nanoscale of the functional material and the domains, diverse types of twinning, stacking faults, and the possible presence of the rock salt phase. Determining the phase ratio from transmission electron microscopy imaging can only be done for thin regions near the surfaces of the crystals, and the intense beam that is needed for imaging induces the same transformation to spinel as cycling does. In this article, it is demonstrated that the low electron dose sufficient for electron diffraction allows the collection of data without inducing a phase transformation. Using calculated electron diffraction patterns, we demonstrate that it is possible to determine the volume ratio of the different phases in the particles using a pair-wise comparison of the intensities of the reflections. Using this method, the volume ratio of spinel structure to honeycomb layered structure is determined for a submicron sized crystal from experimental three-dimensional electron diffraction (3D ED) and precession electron diffraction (PED) data. Both twinning and the possible presence of the rock salt phase are taken into account. After 150 charge–discharge cycles, 4% of the volume in LR-NMC particles was transformed irreversibly from the honeycomb layered structure to the spinel structure. The proposed method would be applicable to other multi-phase materials as well.https://www.mdpi.com/2073-8994/13/11/19893D EDPEDNMCphase ratiobattery |
| spellingShingle | Matthias Quintelier Tyché Perkisas Romy Poppe Maria Batuk Mylene Hendrickx Joke Hadermann Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction Symmetry 3D ED PED NMC phase ratio battery |
| title | Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction |
| title_full | Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction |
| title_fullStr | Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction |
| title_full_unstemmed | Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction |
| title_short | Determination of Spinel Content in Cycled Li<sub>1.2</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>Co<sub>0.13</sub>O<sub>2</sub> Using Three-Dimensional Electron Diffraction and Precession Electron Diffraction |
| title_sort | determination of spinel content in cycled li sub 1 2 sub ni sub 0 13 sub mn sub 0 54 sub co sub 0 13 sub o sub 2 sub using three dimensional electron diffraction and precession electron diffraction |
| topic | 3D ED PED NMC phase ratio battery |
| url | https://www.mdpi.com/2073-8994/13/11/1989 |
| work_keys_str_mv | AT matthiasquintelier determinationofspinelcontentincycledlisub12subnisub013submnsub054subcosub013subosub2subusingthreedimensionalelectrondiffractionandprecessionelectrondiffraction AT tycheperkisas determinationofspinelcontentincycledlisub12subnisub013submnsub054subcosub013subosub2subusingthreedimensionalelectrondiffractionandprecessionelectrondiffraction AT romypoppe determinationofspinelcontentincycledlisub12subnisub013submnsub054subcosub013subosub2subusingthreedimensionalelectrondiffractionandprecessionelectrondiffraction AT mariabatuk determinationofspinelcontentincycledlisub12subnisub013submnsub054subcosub013subosub2subusingthreedimensionalelectrondiffractionandprecessionelectrondiffraction AT mylenehendrickx determinationofspinelcontentincycledlisub12subnisub013submnsub054subcosub013subosub2subusingthreedimensionalelectrondiffractionandprecessionelectrondiffraction AT jokehadermann determinationofspinelcontentincycledlisub12subnisub013submnsub054subcosub013subosub2subusingthreedimensionalelectrondiffractionandprecessionelectrondiffraction |