Perennially frozen soil in high latitude ecosystems (permafrost) currently stores 1330-1580 Pg of carbon (C). As these ecosystems warm, the thaw and decomposition of permafrost is expected to release large amounts of C to the atmosphere. Fortunately, losses from the permafrost C pool will be partially offset by increased plant productivity. The degree to which plants are able to sequester C, however, will be determined by changing nitrogen (N) availability in these thawing soil profiles. N availability currently limits plant productivity in tundra ecosystems but plant access to N is expected improve as decomposition increases in speed and extends to deeper soil horizons. To evaluate the relationship between permafrost thaw and N availability, we monitored N cycling during 5 years of experimentally induced permafrost thaw at the Carbon in Permafrost Experimental Heating Research (CiPEHR) project. Inorganic N availability increased significantly in response to deeper thaw and greater soil moisture induced by Soil warming. This treatment also prompted a 23% increase in aboveground biomass and a 49% increase in foliar N pools. The sedge Eriophorum vaginatum responded most strongly to warming: this species explained 91% of the change in aboveground biomass during the 5 year period. Air warming had little impact when applied alone, but when applied in combination with Soil warming, growing season soil inorganic N availability was significantly reduced. These results demonstrate that there is a strong positive relationship between the depth of permafrost thaw and N availability in tundra ecosystems but that this relationship can be diminished by interactions between increased thaw, warmer air temperatures, and higher levels of soil moisture. Within 5 years of permafrost thaw, plants actively incorporate newly available N into biomass but C storage in live vascular plant biomass is unlikely to be greater than losses from deep soil C pools.
In the present work, an alternative to the standard ex-situ and destructive focused ion beam scanning electron microscopy (FIB/SEM) analysis procedure is demonstrated for monitoring the morphological degradation of a single Si/graphite (1/1 mass ratio) blended electrode for Li-ion batteries. For this purpose, a FIB milled microcavity is created in the pristine electrode, which is observed in FIB-polished cross section by SEM at different cycling periods (pristine, 1 st , 9 th and 50 th cycles). This allows studying the same cycled electrode as for an in-situ method. Its cyclinginduced morphological change is characterized at the electrode and particle scales by monitoring the evolution of the electrode thickness, mass and porosity, the Si particle morphology, Si interparticle distance, surface fraction and twisting of the graphite flakes. This is correlated to the evolution of the electrode discharge capacity and impedance. As a result, a more comprehensive view of the degradation phenomena of the Si/graphite blended electrode is established.
The conception of cheaper and greener electrode materials is critical for lithium (Li)‐ion battery manufacturers. In this study, a by‐product of the carbothermic reduction of SiO2 to Si, containing 65 wt% Si, 31 wt% SiC, and 4 wt% C, is evaluated as raw material for the production of high‐capacity anodes for Li‐ion batteries. After 20 h of high‐energy ball milling, C is fully converted to SiC and a micrometric powder (D50 ∼1 μm) is obtained in which submicrometric SiC inclusions are embedded in a nanocrystalline/amorphous Si matrix. This material is able to maintain a capacity >1000 mAh g−1 (>3 mAh cm−2) over 100 cycles. No crystalline Li15Si4 phase is formed upon cycling as shown from the differential dQ/dV curves. The good mechanical resiliency of the electrode is evidenced by monitoring its morphological changes from sequential focused ion beam scanning electron microscopy analyses. However, a progressive and irreversible increase in the electrode mass and thickness is observed over cycling (reaching 125% and 60% after 200 cycles, respectively), which is mainly attributed to the accumulation of solid electrolyte interphase products in the electrode.
Silicon is mainly produced by carbothermic reduction of silica. This process generates a by-product called silicon slag, which consists mainly of a mixture of Si, SiC and C. This silicon slag represents considerable energy and material losses. On the other hand, the production of cheaper and more environmentally friendly electrode materials is essential for Li-ion battery manufacturers. In this study, it is demonstrated that this waste containing 65 wt% Si, 31 wt% SiC and 4 wt% C can be valorized as low-cost high-capacity LiB anode material. After 20 h of high-energy ball-milling, C is fully converted to SiC and a micrometric powder is obtained in which submicrometric SiC inclusions are embedded in a nanocrystalline/amorphous Si matrix (Fig. 1a). This material displays a specific discharge capacity ≥1100 mAh g-1 at a current density ≤ 0.9 A g-1 (Fig. 1b) and an areal capacity ≥3.5 mAh cm-2 for at least 100 cycles (Fig. 1c). Moreover, calendering has no negative impact on the electrode performance (Fig 1d). The dQ/dV curves (Fig. 1e) do not shown intense-sharp anodic peak at about 0.45V characteristic of the delithiation of the c-Li15Si4 phase, suggesting that its formation is here prevented. This may be beneficial for the electrode cycle life as the formation of c-Li15Si4 phase is well-known to accentuate the particle cracking. However, a progressive and irreversible increase of the electrode mass and thickness is observed over cycling (reaching 125% and 60% after 200 cycles, respectively) (Fig. 1f), which is mainly attributed to the accumulation of solid electrolyte interphase (SEI) products in the electrode. Figure 1
The conception of cheaper and greener electrode materials is critical for Li-ion battery manufacturers. In this study, it is shown that a by-product of the carbothermic reduction of SiO2 to Si, containing Si, SiC and C materials, can be valorized as a low-cost and high-capacity anode material for Li-ion batteries after an appropriate high-energy ball milling treatment. The latter results in the production of a micrometric powder (D50 ~1 mm) in which submicrometric SiC inclusions are embedded in a nanocrystalline/amorphous Si matrix. Such a microstructure prevents the deleterious formation of c-Li15Si4 phase, which is well known to accentuate particle cracking. As a result, the electrode is able to maintain a capacity >1000 mAh g-1 (>3 mAh cm-2) over 100 cycles. Moreover, calendering has no negative impact on the electrode performance. However, a significant and irreversible increase of the electrode mass and thickness was observed over cycling, which is mainly attributed to the accumulation of SEI products. In order to have deeper insights into the microstructural evolution of the electrode during cycling, a focused ion beam (FIB) milled microcavity (45×20×50 µm3) was created in the center of the pristine electrode. This cavity was observed by SEM at different cycling periods of a single electrode (Fig. 1a). This investigation method allows following the same electrode along different steps of its cycling, nearly as for an in-situ method. Additionally, backscattered-electron (BSE) imaging was performed on broad ion beam (BIB) polished cross-section of the electrode after different periods of cycling (Fig. 1b). The morphological change is characterized at the electrode and particle scales by monitoring the thickness, mass, porosity and macrocracking of the electrode, SEI layer thickness and particle morphology. On the basis of these investigations, a more comprehensive view of the degradation phenomena of the electrode is established. Figure 1
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