Synthesis and Characterization of a Multication Doped Mn Spinel, LiNi_0.3Cu_0.1Fe_0.2Mn_1.4O₄, as 5 V Positive Electrode Material

Abstract

The suitability of multication doping to stabilize the disordered Fd 3̅ m structure in a spinel is reported here. In this work, LiNi 0.3 Cu 0.1 Fe 0.2 Mn 1.4 O 4 was synthesized via a sol–gel route at a calcination temperature of 850 °C. LiNi 0.3 Cu 0.1 Fe 0.2 Mn 1.4 O 4 is evaluated as positive electrode material in a voltage range between 3.5 and 5.3 V (vs Li + /Li) with an initial specific discharge capacity of 126 mAh g –1 at a rate of C /2. This material shows good cycling stability with a capacity retention of 89% after 200 cycles and an excellent rate capability with the discharge capacity reaching 78 mAh g –1 at a rate of 20 C . In operando X-ray diffraction (XRD) measurements with a laboratory X-ray source between 3.5 and 5.3 V at a rate of C /10 reveal that the (de)lithiation occurs via a solid-solution mechanism where a local variation of lithium content is observed. A simplified estimation based on the in operando XRD analysis suggests that around 17–31 mAh g –1 of discharge capacity in the first cycle is used for a reductive parasitic reaction, hindering a full lithiation of the positive electrode at the end of the first discharge.

Kinetic Control of Long‐Range Cationic Ordering in the Synthesis of Layered Ni‐Rich Oxides

“…In operando X‐ray powder diffraction (XRD) [ 48 ] was used to unveil the influence of long‐range cation mixing on the structural evolution of the as‐synthesized cathode materials (LNCM622O‐700, LNCM622O‐800, and LNCM622O‐900) during electrochemical cycling. Figure shows the contour plots of the evolution of 003, 018, and 110 reflections for three electrodes during the first charge–discharge process.…”

Li+/Na+ Ion Exchange in Layered Na2/3(Ni0.25Mn0.75)O2: A Simple and Fast Way to Synthesize O3/O2-Type Layered Oxides

“…For further elucidation of the structural degradation mechanism of layered Li 2/3 □ 1/3 (Ni 0.25 Mn 0.75 )­O 2 electrodes upon cycling, in situ XRD patterns of both Li/NNMO-P3 and Li/NNMO-P2 cells were recorded on a STOE X-ray diffractometer with Ag Kα 1 radiation . The in situ coin cells were first discharged to 2.0 V and then galvanostatically cycled in a narrow voltage range of 2.0–4.3 V, as shown in Figure and Figures S11 and S12.…”

Managing Life Span of High-Energy LiNi0.88Co0.11Al0.01O2|C–Si Li-Ion Batteries

“…In operando XRD measurements were performed using a dedicated in operando setup. 13 The diffractometer has a Ag X-ray tube (λ = 0.55941 Å) with a focusing Ge 111 monochromator and two Mythen 1D silicon strip detectors. The cathode was cycled against lithium metal at a rate of C/10 between 3.0 and 4.25 V using a galvanostatic Structural refinements were carried out by the Rietveld method using FullProf software.…”

“…Before performing ex situ XRD experiments, the anodes of types A and B (at BoL) were prelithiated at a rate of C/10. A dedicated coin cell with a 75 μm Kapton foil window was used as a sample container to avoid air contact . As opened and ex situ XRD experiments were performed using Mo Kα 1 radiation (λ = 0.70932 Å) in a transmission geometry at a STOE STADI/P diffractometer (Ge 111 monochromator, Mythen 1D silicon strip detector).…”

“…In operando XRD measurements were performed using a dedicated in operando setup . The diffractometer has a Ag X-ray tube (λ = 0.55941 Å) with a focusing Ge 111 monochromator and two Mythen 1D silicon strip detectors.…”