This review provides a comprehensive overview about the “hidden champion” of lithium-ion battery technology – graphite.
Conversion/alloying materials (CAMs) provide substantially higher specific capacities than graphite, the state‐of‐the‐art lithium‐ion battery anode material. The ability to host much more lithium per unit weight and volume is, however, accompanied by significant volume changes, which challenges the realization of a stable solid electrolyte interphase (SEI). Herein, the comprehensive characterization of the composition and evolution of the SEI on transition metal (TM) doped zinc oxide as CAM model compound, is reported, with a particular focus on the impact of the TM dopant (Fe or Co). The results unveil that the presence of iron specifically triggers the electrolyte decomposition. However, this detrimental effect can be avoided by stabilizing the interface with the electrolyte by a carbonaceous coating. These findings provide a great leap forward toward the enhanced understanding of such doped materials and (transition) metal oxide active materials in general.
In order to further improve the energy and power density of state-of-the-art lithium-ion batteries (LIBs), new cell chemistries and, therefore, new active materials with alternative storage mechanisms are needed. Herein, we report on the structural and electrochemical characterization of Fe-doped ZnO samples with varying dopant concentrations, potentially serving as anode for LIBs (Rechargeable lithium-ion batteries). The wurtzite structure of the Zn1−xFexO samples (with x ranging from 0 to 0.12) has been refined via the Rietveld method. Cell parameters change only slightly with the Fe content, whereas the crystallinity is strongly affected, presumably due to the presence of defects induced by the Fe3+ substitution for Zn2+. XANES (X-ray absorption near edge structure) data recorded ex situ for Zn0.9Fe0.1O electrodes at different states of charge indicated that Fe, dominantly trivalent in the pristine anode, partially reduces to Fe2+ upon discharge. This finding was supported by a detailed galvanostatic and potentiodynamic investigation of Zn1−xFexO-based electrodes, confirming such an initial reduction of Fe3+ to Fe2+ at potentials higher than 1.2 V (vs. Li+/Li) upon the initial lithiation, i.e., discharge. Both structural and electrochemical data strongly suggest the presence of cationic vacancies at the tetrahedral sites, induced by the presence of Fe3+ (i.e., one cationic vacancy for every two Fe3+ present in the sample), allowing for the initial Li+ insertion into the ZnO lattice prior to the subsequent conversion and alloying reaction.
Iron‐doped tin oxide (Sn0.9Fe0.1O2), and specifically carbon‐coated Sn0.9Fe0.1O2 (Sn0.9Fe0.1O2‐C) provides high reversible capacity and a reasonably low de‐/lithiation potential owing to the combined conversion and alloying mechanism. The initial (quasi‐)amorphization during the first lithiation, however, renders an in‐depth understanding of the reaction mechanism challenging. Herein, a comprehensive investigation via a set of highly complementary characterization techniques is reported, including operando X‐ray diffraction, ex situ 119Sn and 57Fe Mössbauer spectroscopy, ex situ 7Li NMR spectroscopy, operando isothermal microcalorimetry (IMC) of Li‖Sn0.9Fe0.1O2‐C coin cells, and electrochemical microcalorimetry of single Sn0.9Fe0.1O2‐C electrodes. The combination of these advanced techniques allows for detailed insights into the lithiation and delithiation mechanism and the potential determining processes, despite the (quasi‐) amorphous nature of the active material after the initial lithiation.
Experimentalists and theoreticians commonly prefer single‐phase materials for their studies, since this allows for a direct correlation of the findings obtained and the compound studied. For the design of high‐performance materials for energy applications, however, mixtures of different phases frequently reveal an advanced set of desired properties. Recently, it has been shown that a combination of different phases, that is, P2/P3/O3‐ NaxMn0.5Ni0.3Fe0.1Mg0.1O2, allows for higher capacities and enhanced cycling stability when employed as sodium‐on cathode compared to pure P2‐NaxMn0.7Ni0.1Fe0.1Mg0.1O2 or O3‐type NaxMn0.5Ni0.3Fe0.1Mg0.1O2. Herein, the in‐depth comparative investigation of these three materials is presented via in situ X‐ray diffraction and X‐ray absorption spectroscopy coupled with electrochemical techniques to fully elucidate the origin of this superior performance. In fact, it appears that the redox activity or inactivity of the manganese cation plays a decisive role for the reversibility of the sodium‐ion uptake and release.
Purpose Identifying anatomical risk factors on recurrent dislocation after medial reefing is important for deciding surgical treatment. The present study aimed to retrospectively analyze the preoperative magnetic resonance imaging (MRI)-based parameters of patients treated with medial reefing and whether these parameters lead to a higher risk of recurrent dislocation. Methods Fifty-five patients (18.6 ± 6.6 years) who underwent medial reefing after primary traumatic patellar dislocation (84% with medial patellofemoral ligament [MPFL] rupture) were included. Patients were followed up for at least 24 months postoperatively (3.8 ± 1.2 years) to assess the incidence of recurrent patellar dislocation. In patients without recurrent dislocation, the Kujala and subjective IKDC scores were assessed. Moreover, the tibial tubercle-trochlear groove (TT-TG), sulcus angle, patellar tilt, patellar shift, and lateral trochlea index (LTI) were measured. The patellar height was measured using the Caton-Dechamps (CDI), Blackburne-Peel (BPI), and Insall-Salvati index (ISI). The cohort was subclassified into two groups with and without recurrent dislocation. Differences between groups were analyzed with respect to the MRI parameters. Results Forty percent had a pathological sulcus angle of > 145°, 7.2% had an LTI of < 11°, 47.3% had a patellar tilt of > 20°, and 36.4% had a TT-TG of ≥ 16 mm. Increased patellar height was observed in 34.5, 65.5, and 34.5% of the patients as per CDI, BPI, and ISI, respectively. Nineteen (34.5%) patients suffered from recurrent dislocation. Compared with patients without recurrent dislocation, those with recurrent dislocation had a significantly lower LTI (p = 0.0467). All other parameters were not significantly different between the groups. Risk factor analysis showed higher odds ratios (OR > 2), although not statistically significant, for MPFL rupture (OR 2.05 [95% confidence interval 0.38–11.03], LTI (6.6 [0.6–68.1]), TT-TG (2.9 [0.9–9.2]), and patellar height according to ISI (2.3 [0.7–7.5]) and CDI (2.3 [0.7–7.5])). Patients without recurrent dislocation had a Kujala score of 93.7 ± 12.1 (42–100) points and an IKDC score of 90.6 ± 11.7 (55.2–100) points. Conclusion Anatomical, MRI-based parameters should be considered before indicating medial reefing. A ruptured MPFL, an LTI < 11°, a TT-TG ≥ 16 mm, a patellar tilt > 20 mm, and an increased patellar height according to ISI and CDI were found to be associated, although not significantly, with a higher risk (OR > 2) of recurrent patellar dislocation after medial reefing. Thorough preoperative analysis is crucial to reduce the risk of recurrent dislocation in young patient cohorts. Level of evidence Level IV
High-capacity lithium-ion anodes such as alloying-, conversion-, and conversion/alloying-type materials are subjected to extensive volume variation upon lithiation/delithiation. However, a careful examination of these processes at the particle and electrode level as well as the impact of the kind of lithium-ion uptake mechanism is still missing. Herein, we investigated the volume variation upon lithiation/delithiation for a series of conversion/alloying materials with a varying relative contribution of the alloying and conversion reaction, i.e., carbon-coated ZnFe2O4, Zn0.9Fe0.1O, and Sn0.9Fe0.1O2 by operando dilatometry and ex situ scanning electron microscopy of the electrode cross section. While the theoretical estimation at the particle level indicates a rather large volume expansion of 113% (ZnFe2O4) and more, the true volume variation on the electrode level reveals very limited changes of only around 11% (ZnFe2O4). Combining the experimental findings with some theoretical considerations highlights the (to a certain extent unexpected) impact of the initial electrode porosity.
Sodium-ion batteries (SIBs) are promising alternative to Lithium-ion batteries for massive stationary energy storage. To improve energy density, however, more performing active materials are needed. In order to allow sustainable scale-up, it is also mandatory to develop green products and processes. Herein, we report on anodes of phosphorus/carbon (P/C) nanocomposites prepared via High Energy Ball Milling (HEBM), a simple, powerful and easily scalable synthesis technique. The electrodes were prepared under oxygen-free atmosphere, using water as solvent, which enabled the use of aluminum (instead of copper) as current collector, implying significant cost reduction. The P/C nanocomposite obtained after 54 hours HEBM resulted in excellent cycling stability, delivering very high specific capacity (2200 mAh g -1 , C/20) and showing good capacity retention after 120 cycles. A careful structural analysis (XRD, FESEM-EDS, XPS), revealed that long milling times strongly increased cycling stability due to: i) significant decrease of P particle size inside the matrix and deep composite amorphization, which alleviates the buffering dimensional issues typical of black phosphorus; ii) presence of defects in the carbonaceous component, which allows easier Na + insertion into the anode. Our results show that P/C nanocomposites are very promising anode materials for SIBs, paving the way for further exploitation of nano-architectures in SIBs technology.
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