# Fileset

[jp5c02329_si_001.pdf](https://mdr.nims.go.jp/filesets/e7e18157-fb2d-4ae8-a277-d9dbe1131b51/download)

## Creator

Fumihiko Ichihara, [Shogo Miyoshi](https://orcid.org/0000-0003-0375-1187), [Machiko Ode](https://orcid.org/0000-0002-9500-5466), [Takuya Masuda](https://orcid.org/0000-0001-7462-2177)

## Rights

[Creative Commons BY Attribution 4.0 International](https://creativecommons.org/licenses/by/4.0/)

## Other metadata

[Co-sintering Reaction Analysis of LiCoO<sub>2</sub> Cathodes and NASICON-Type LATP Solid Electrolytes Studied by Experimental and Computational Methods](https://mdr.nims.go.jp/datasets/363d5ebb-27af-4907-9226-27020c614609)

## Fulltext

S1Supporting InformationCo-sintering Reaction Analysis of LiCoO2 Cathodes and NASICON-Type LATP Solid Electrolytes Studied by Experimental and Computational MethodsFumihiko Ichihara†, Shogo Miyoshi†, Machiko Ode‡ and Takuya Masuda*†§† Research Center for Energy and Environmental Materials, National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0044, Japan.‡ Research Center for Structural Materials, National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0047, Japan.§ Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, Hokkaido 060-0810, Japan.S21.  XRD data analysisTable S1. Powder diffraction files for Rietveld analysis.Chemical Species Chemical FormulaCrystal StructurePowder Diffraction File card number ICSDLithium cobalt oxide LiCoO2 R-3m 01-070-2685 51182Lithium dititanium tris(phosphate(V)) LiTi2(PO4)3 R-3c 01-072-6140 95979Cobalt oxide Co3O4 Fd-3m 01-076-1802 36256Lithiophosphate Li3PO4 Pmnb 01-087-0039 50058Cobalt titanium oxide CoTiO3 R-3h 01-077-1373 48107Titanium oxide, rutile TiO2 P42/mnm 01-070-7347 093097Lithium cobalt phosphate(V), olivine LiCoPO4 Pnma 01-089-6192 87422Dicobalt titanium Oxide Co2TiO4 Fd-3m 01-080-1671 69506Dilithium titanate Li2TiO3 C2/c 01-080-7162 261238S3Figure S1.  Results of Rietveld analysis of XRD patterns derived from LCLA37. S4Figure S2.  Results of Rietveld analysis of XRD patterns derived from LCLA55. S5Figure S3.  Results of Rietveld analysis of XRD patterns derived from LCLA73.S62. XANES data analysisTable S2. Principal component analysis results for Co K-edge XANES spectra of LCLA37.Components Eigenvalues Variance Cumulative variance1 13.22671 0.944765 0.9447652 0.745323 0.053237 0.9980033 0.026473 0.001891 0.9998934 0.000819 0.000059 0.9999525 0.000374 0.000027 0.9999796 0.000167 0.000012 0.9999917 0.000108 0.000008 0.9999988 0.000009 0.000001 0.9999999 0.000006 0 0.99999910 0.000004 0 111 0.000002 0 112 0.000001 0 113 0.000001 0 114 0 0 1Table S3. Co standard compounds target transformation results of LCLA37 for LCF.Target materials Mean squared errorLCO 4.11689E-5Co3O4 3.34936E-4CoTiO3 2.54132E-4LiCoPO4 4.1102E-4Co2TiO4 0.00201CoO 0.00419Co(OH)2 0.0016Co(NO3)2_6H2O 0.00927Co2P 0.01831Co metal 0.01437CoCO3 0.00716CoCl2 0.00864CoO(OH) 0.00202Co3(PO4)2_8H2O 0.00534S7Table S4. Principal component analysis results for Ti K-edge XANES spectra of LCLA37.Components Eigenvalues Variance Cumulative variance1 13.95546 0.996819 0.9968192 0.040105 0.002865 0.9996843 0.003562 0.000254 0.9999394 0.000565 0.00004 0.9999795 0.000168 0.000012 0.9999916 0.000089 0.000006 0.9999977 0.000018 0.000001 0.9999998 0.00001 0.000001 0.9999999 0.000003 0 110 0.000002 0 111 0.000002 0 112 0.000001 0 113 0.000001 0 114 0 0 1Table S5. Ti standard compounds target transformation results of LCLA37 for LCF.Target materials Mean squared errorLATP 8.4675E-6Rutile-TiO2 1.66967E-4CoTiO3 7.46717E-4Co2TiO4 0.00252Amorphous-TiO2 0.00105Anatase-TiO2 0.00116Li4Ti5O12 0.00123Li2TiO3 0.00671Ti2O3 0.05307Ti metal 0.05634S8Table S6. Principal-Component Analysis Results for Co K-edge XANES spectra of LCLA55.Components Eigenvalues Variance Cumulative variance1 13.85197 0.989426 0.9894262 0.136191 0.009728 0.9991543 0.011375 0.000812 0.9999674 0.00032 0.000023 0.9999895 0.000065 0.000005 0.9999946 0.000057 0.000004 0.9999987 0.00001 0.000001 0.9999998 0.000005 0 0.9999999 0.000004 0 110 0.000002 0 111 0.000001 0 112 0.000001 0 113 0.000001 0 114 0 0 1Table S7. Co standard compounds target transformation results of LCLA55 for LCF.Target materials Mean squared errorLCO 1.08E-05Co3O4 2.43E-04CoTiO3 0.00131LiCoPO4 0.00305Co2TiO4 4.74E-4CoO 0.00453Co(OH)2 0.01189Co(NO3)2_6H2O 0.00522Co2P 0.01242Co metal 0.01001CoCO3 0.01208CoCl2 0.00576CoO(OH) 0.00157Co3(PO4)2_8H2O 0.00995S9Table S8. Principal-Component Analysis Results for Ti K-edge XANES spectra of LCLA55.Components Eigenvalues Variance Cumulative variance1 13.92416 0.994583 0.9945832 0.067259 0.004804 0.9993873 0.005965 0.000426 0.9998144 0.00177 0.000126 0.999945 0.000554 0.00004 0.999986 0.000157 0.000011 0.9999917 0.000063 0.000005 0.9999958 0.000038 0.000003 0.9999989 0.00001 0.000001 0.99999910 0.000006 0 0.99999911 0.000005 0 0.99999912 0.000004 0 113 0.000002 0 114 0.000001 0 1Table S9. Ti standard compounds target transformation results of LCLA55 for LCF.Target materials Mean squared errorLATP 1.73E-05Rutile-TiO2 2.18E-04CoTiO3 3.00E-04Amorphous-TiO2 0.0015Anatase-TiO2 0.00368Li4Ti5O12 8.21E-04Co2TiO4 4.23E-4Li2TiO3 0.00255Ti2O3 0.04354Ti metal 0.04925S10Table S10. Principal-Component Analysis Results for Co K-edge XANES spectra of LCLA73.Components Eigenvalues Variance Cumulative variance1 13.96701 0.997644 0.9976442 0.032096 0.002293 0.9999363 0.000597 0.000043 0.9999794 0.000238 0.000017 0.9999965 0.000035 0.000003 0.9999986 0.000017 0.000001 17 0.000002 0 18 0.000002 0 19 0.000001 0 110 0.000001 0 111 0 0 112 0 0 113 0 0 114 0 0 1Table S11. Co standard compounds target transformation results of LCLA73 for LCF.Target materials Mean squared errorLCO 7.65E-06Co3O4 2.42E-04CoTiO3 0.0128LiCoPO4 0.0163Co2TiO4 0.0023CoO 0.00645Co(OH)2 0.02761Co(NO3)2_6H2O 0.01655Co2P 0.02454Co metal 0.02086CoCO3 0.02864CoCl2 0.01176CoO(OH) 0.01015Co3(PO4)2_8H2O 0.02636S11Table S12. Principal-Component Analysis Results for Ti K-edge XANES spectra of LCLA73.Components Eigenvalues Variance Cumulative variance1 13.91641 0.994029 0.9940292 0.072999 0.005214 0.9992433 0.007422 0.00053 0.9997734 0.003042 0.000217 0.9999915 0.00005 0.000004 0.9999946 0.000033 0.000002 0.9999967 0.00002 0.000001 0.9999988 0.000011 0.000001 0.9999999 0.000007 0.000001 0.99999910 0.000004 0 0.99999911 0.000003 0 112 0.000003 0 113 0.000001 0 114 0.000001 0 1Table S13. Ti standard compounds target transformation results of LCLA73 for LCF.Target materials Mean squared errorLATP 1.33E-05Rutile-TiO2 0.00396CoTiO3 0.00151Amorphous-TiO2 0.00139Anatase-TiO2 0.00199Li4Ti5O12 5.29E-04Co2TiO4 0.00117Li2TiO3 5.55E-04Ti2O3 0.04194Ti metal 0.04412S122.1. LCF of XANES spectraFigure S4.  Results of linear combination fitting of the Co K-edge XANES spectra derived from LCLA37.S13Figure S5.  Results of linear combination fitting of the Ti K-edge XANES spectra derived from LCLA37.S14Figure S6.  Results of linear combination fitting of the Co K-edge XANES spectra derived from LCLA55.S15Figure S7.  Results of linear combination fitting of the Ti K-edge XANES spectra derived from LCLA55.S16Figure S8.  Results of linear combination fitting of the Co K-edge XANES spectra derived from LCLA73.S17Figure S9.  Results of linear combination fitting of the Ti K-edge XANES spectra derived from LCLA73.S183. Ordered and disordered Li4-2xCo3xTi5-xO12 spinel structure and Co2TiO4 spinel structureFigure S10. (a) Co K-edge and (b) Ti K-edge XANES spectra of ordered and disordered Li4-2xCo3xTi5-xO12 spinel structure and Co2TiO4 spinel structure.Figure S11.  XRD patterns of ordered and disordered Li4-2xCo3xTi5-xO12 spinel structure and Co2TiO4 spinel structure.Co2TiO4 was prepared by solid-state reaction method using stoichiometric amount of Co3O4 and TiO2 powder. The mixture of Co3O4 and TiO2 was grinded in a zirconia mortar and pestle and pressed at 2 t/cm2 in a uniaxial die with a 10 mm diameter to produce a pellet. The pellet was sintered at 1200 °C for 12 h in air.S194. Thermal stability of pure LCO and LATP tested by XRD and XANESFigure S12.  (a) X-ray diffraction patterns and (b) normalized Co K-edge XANES spectra of LCO sintered at various temperatures.Figure S13.  (a) X-ray diffraction patterns and (b) normalized Ti K-edge XANES spectra of LATP sintered at various temperatures.S205. Spinel phase in LCLA55 and LCLA73Figure S14.  Total amount of Co and Ti cations in LCLA55 calculated for spinel phase as (a) Li4Ti5O12 and (b) Co2TiO4Figure S15.  Enlarged the diffraction peaks derived from spinel phases of (a)LCLA55 and (b)LCLA73.S216. Thermodynamics calculation by FactSage 8.2Table S14. Reaction products observed in experiments and predicted by thermodynamic calculation. (Reaction products written in black color are the reaction products matched by experiment and calculation. Reaction products written in gray color are those calculated as high-temperature phases. Reaction products written in blue color are reaction products considered to be observed as solid solution. Reaction products written in red are those that did not match between experiments.)S227. LCLA37 sintering experiments with varying sintering time and particle size.Figure S16.  XRD patterns and Rietveld analysis results of LCLA37 sintered at (a) 500°C, (b) 600°C and (c) 700°C for 8 hours and 2 weeks. XRD patterns and Rietveld analysis results of LCLA55 sintered at (d) 500°C, (e) 600°C and (f) 700°C for 8 hours and 2 weeks. XRD patterns and Rietveld analysis results of LCLA73 sintered at (g) 500°C, (h) 600°C and (i) 700°C for 8 hours and 2 weeks. The Rietveld analysis results are shown together with the thermodynamic calculation (TDC) results and the thermodynamic calculation results without the high temperature phase (TDC w/o HT).S23Figure S17. (a) SEM image of (a) fine and (b) regular grain LATP.Figure S18. XRD patterns and Rietveld analysis results of LCLA37 sintered at (a) 500°C, (b) 600°C and (c) 700°C using fine and regular grain LATP. The Rietveld analysis results are shown together with the thermodynamic calculation (TDC) results and the thermodynamic calculation results without the high temperature phase (TDC w/o HT).S248. Molar amount of thermodynamically stable phase of LCLA55Figure S19. (a) Molar amount of thermodynamically stable phase of LCLA55 after replacing LiCoPO4, Li2CoTi3O8 and 4CoO with Li3PO4 and 3Co2TiO4 and (b) subsequent conversion of the high temperature phase to the low temperature phase.