Hydrothermal-derived carbon as a stabilizing matrix for improved cycling performance of silicon-based anodes for lithium-ion full cells.

In this work, silicon/carbon composites are synthesized by forming an amorphous carbon matrix around silicon nanoparticles (Si-NPs) in a hydrothermal process. The intention of this material design is to combine the beneficial properties of carbon and Si, i.e., an improved specific/volumetric capacity and capacity retention compared to the single materials when applied as a negative electrode in lithium-ion batteries (LIBs). This work focuses on the influence of the Si content (up to 20 wt %) on the electrochemical performance, on the morphology and structure of the composite materials, as well as the resilience of the hydrothermal carbon against the volumetric changes of Si, in order to examine the opportunities and limitations of the applied matrix approach. Compared to a physical mixture of Si-NPs and the pure carbon matrix, the synthesized composites show a strong improvement in long-term cycling performance (capacity retention after 103 cycles: ≈55% (20 wt % Si composite) and ≈75% (10 wt % Si composite)), indicating that a homogeneous embedding of Si into the amorphous carbon matrix has a highly beneficial effect. The most promising Si/C composite is also studied in a LIB full cell vs a NMC-111 cathode; such a configuration is very seldom reported in the literature. More specifically, the influence of electrochemical prelithiation on the cycling performance in this full cell set-up is studied and compared to non-prelithiated full cells. While prelithiation is able to remarkably enhance the initial capacity of the full cell by ≈18 mAh g-1, this effect diminishes with continued cycling and only a slightly enhanced capacity of ≈5 mAh g-1 is maintained after 150 cycles.

Running out of lithium? A route to differentiate between capacity losses and active lithium losses in lithium-ion batteries.

Active lithium loss (ALL) resulting in a capacity loss (QALL), which is caused by lithium consuming parasitic reactions like SEI formation, is a major reason for capacity fading and, thus, for a reduction of the usable energy density of lithium-ion batteries (LIBs). QALL is often equated with the accumulated irreversible capacity (QAIC). However, QAIC is also influenced by non-lithium consuming parasitic reactions, which do not reduce the active lithium content of the cell, but induce a parasitic current. In this work, a novel approach is proposed in order to differentiate between QAIC and QALL. The determination of QALL is based on the remaining active lithium content of a given cell, which can be determined by de-lithiation of the cathode with the help of the reference electrode of a three-electrode set-up. Lithium non-consuming parasitic reactions, which do not influence the active lithium content have no influence on this determination. In order to evaluate this novel approach, three different anode materials (graphite, carbon spheres and a silicon/graphite composite) were investigated. It is shown that during the first charge/discharge cycles QALL is described moderately well by QAIC. However, the difference between QAIC and QALL rises with increasing cycle number. With this approach, a differentiation between "simple" irreversible capacities and truly detrimental "active Li losses" is possible and, thus, Coulombic efficiency can be directly related to the remaining useable cell capacity for the first time. Overall, the exact determination of the remaining active lithium content of the cell is of great importance, because it allows a statement on whether the reduction in lithium content is crucial for capacity fading or whether the fading is related to other degradation mechanisms such as material or electrode failure.