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Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is The Royal Society of Chemistry 2022Supporting Information for the articleOn the electrochemical properties of the Fe-Ti dopedLNMO material LiNi0.5Mn1.37Fe0.1Ti0.03O3.95Pirmin Stüblea,b, Holger Geßweina, Sylvio Indrisa, Marcus Müllera, and Joachim R. Binderaa: Institute for Applied Materials, Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen, Germanyb: Helmholtz Institute Ulm, 89081 Ulm, GermanyTable S1: Detailed Information on thermal treatment of all LNMFTO samples and specific surface area of thepristine LNMFTO (A2) and the fast cooled samples FC450 to FC940, according to the BET theory. Specificsurface area measurements of the SC samples were omitted, since changes of the particle morphology are veryunlikely to occur with slow cooling at temperatures 650 C.Sample StartingThermal TreatmentSpecificSurface (BET)A2A1RT –300 K/h 900 C (20 h) –300K/h 600 C (30 h) –300 K/h RT0.82 m²/gFC460A2RT –600 K/h 460 C (20 h) –600K/h RT0.75 m²/gFC500A2RT –600 K/h 500 C (20 h) –600K/h RT0.74 m²/g0.75 m²/gFC540A2RT –600 K/h 540 C (18 h) –600K/h RTFC580A2RT –600 K/h 580 C (16 h) –600K/h RT0.78 m²/gFC620A2RT –600 K/h 620 C (14 h) –600K/h RT0.77 m²/gFC660A2RT –600 K/h 660 C (12 h) –600K/h RT0.79 m²/gFC700A2RT –600 K/h 700 C (10 h) –600K/h RT0.76 m²/gFC740A2RT –600 K/h 740 C (8 h)–600K/h RT0.77 m²/gFC780A2RT –600 K/h 780 C (6 h)–600K/h RT0.78 m²/gFC820A2RT –600 K/h 820 C (5 h)–600K/h RT0.80 m²/gFC860A2RT –600 K/h 860 C (4 h)–600K/h RT0.83 m²/gFC900A2RT –600 K/h 900 C (3 h)–600K/h RT0.83 m²/gFC940A2RT –600 K/h 940 C (2 h)–600K/h RT0.84 m²/gSC460A2RT –600 K/h 460 C (20 h) –10 K/h 350 C –100 K/h RT-SC500A2RT –600 K/h 500 C (20 h) –10 K/h 350 C –100 K/h RT-SC540A2RT –600 K/h 540 C (18 h) –10 K/h 350 C –100 K/h RTSC580A2RT –600 K/h 580 C (16 h) –10 K/h 350 C –100 K/h RT-SC620A2RT –600 K/h 620 C (14 h) –10 K/h 350 C –100 K/h RT-350 C –100 K/h RT-SC660A2RT –600 K/h 660 C (12 h) –10 K/h SC700A2RT –600 K/h 700 C (10 h) –600 K/h 650 C –10 K/h 350 C –100 K/h RT-SC740A2RT –600 K/h 740 C (8 h)350 C –100 K/h RT-–600 K/h 650 C –10 K/h SC780A2RT –600 K/h 780 C (6 h)–600 K/h 650 C –10 K/h 350 C –100 K/h RT-SC820A2RT –600 K/h 820 C (5 h)–600 K/h 650 C –10 K/h 350 C –100 K/h RT-SC860A2RT –600 K/h 860 C (4 h)–600 K/h 650 C –10 K/h 350 C –100 K/h RT-SC900A2RT –600 K/h 900 C (3 h)–600 K/h 650 C –10 K/h 350 C –100 K/h RT-SC940A2RT –600 K/h 940 C (2 h)–600 K/h 650 C –10 K/h 350 C –100 K/h RT-Table S2: Detailed information on the (auxiliary) components of the cathodes (top) and anodes (bottom).ComponentCarbon BlackGraphite (cathode)Binder (PVDF)Graphite (anode)Binder (Na-CMC)Binder (SBR)TypeC-NERGY SUPER C65AGB1010Solef 5130SMG-ACRT 2000 PA7TRD 20011ManufacturerTimcal/Imerys, FranceSuperior Graphite Co., USASolvay, BelgiumHitachi Chemical, JapanDOW Wolff, GermanyJSR Micro, Belgium

Figure S1: Volumetric particle size distribution for the spherical LNMFTO granules obtained from the secondspray drying step (A1) and after the first calcination step (A2). Measurement carried out on a Laser ScatteringParticle Size Distribution Analyzer LA-950 (Horiba).Figure S2: Pore Size distribution of sample A2 obtained from mercury intrusion porosimetry. In accordancewith cross section images of the material, pore diameters of 20 nm to 1500 nm are attributed to pores insideof the spherical granules. From the corresponding pore volume of 62 mm³/g, an internal porosity of 20 % isexpected. (Calculation for LNMFTO-density of 4.2 g/cm³).2

Figure S3: SEM images of the starting material A2 and representative LNMFTO materials calcined attemperatures of 460 C to 940 C (FC460 to FC 940). As desired, all granules have a comparable morphology andthe vast majority of primary particles shows octahedral shape.3

Figure S4: Fe Mößbauer spectrum of sample A2. Experimental data points are shown as white spheres, theoverall fit as blue doublet, and the difference as blue line. Fit parameters used to describe the Fe Mößbauerspectrum are shown in the box: isomer shift (IS), quadrupole splitting (QS), and line width ( ). All values aregiven in mm/s.Figure S5: SEM-EDX analysis of the cross-section of a cathode prepared with starting material A2. Areas withincreased nickel and reduced manganese content can be assigned to the secondary phase. An accumulation ofiron in the secondary phase is not observed. Due to the low titanium concentration, substantial information onits elemental distribution could not be obtained.4

Table S3: Results of the Rietveld refinements for the starting material A2 and the fast and slowly cooledLNMFTO series. The uncertainties of the phase fractions are likely to exceed the specified estimated standarddeviations due to the overlap of main reflections of both phases.RwP[%]Latticeparameter a[pm]LNMFTO (Fd3m)s.o.f.32e(oxygen)PhaseFraction[wt%]Phase Fraction [wt%]A2 (5)6.7(4)Sample 5 LixNi1-xO (R m)

Figure S6: Diffraction patterns and corresponding Rietveld refinement results of the fast (top) and slowlycooled LNMFTO materials (bottom). Selected LNMFTO reflections (space group Fd3m) are labelled in gray andblack. Major reflections of the secondary phase (refined as LixNi1-xO, space group R3m) are marked with greenarrows and indices. Small changes of the weight fraction of the secondary phase can be seen from the enlargedsection around 28.5 . Variations of the lattice parameter of LNMFTO become visible from small shifts of the844 reflection (section around 50.5 ). Double reflections result from Kα1-Kα2-splitting. The black arrows indicatecontributions of the borosilicate and soda lime glass capillaries used.6

Figure S7: Evaluation of the voltage profiles of the second cycles, shown for samples SC660, A2 and FC660 toFC940. The methodology of previous works of Zhong et al.28 was applied. Demarcation lines at 4.375 V and 4.72/ 4.73 V (partially ordered / disordered samples) were chosen to partition the capacity in three regions. Theresults of the evaluation of all samples are listed in the following Table S4.Table S4: Results of the evaluation of the redox profiles of the second cycle, with individual contributions of Niand Mn redox couples and the resulting compositions based on LiNiII0.5-xMnIV1.37-xMnIII2xFe0.1Ti0.03O3.95 .SampleNi4 /Ni3 Ni3 /Ni2 Cap. NitotalMn4 /Mn3 1Ti0.03O3.95LiNi0.48Mn1.39Fe0.1Ti0.03O3.957

1 Supporting Information for the article On the electrochemical properties of the Fe-Ti doped LNMO material LiNi0.5 Mn 1.37 Fe 0.1 Ti0.03 O3.95 Pirmin Stüble a,b, Holger Geßwein a, Sylvio Indris a, Marcus Müllera, and Joachim R. Bindera a: Institute for Applied Materials, Karlsruhe Institu