Sodium‐ion batteries are alternatives for lithium‐ion batteries in applications where cost‐effectiveness is of primary concern, such as stationary energy storage. The stability of sodium‐ion batteries is limited by the current generation of electrolytes, particularly at higher temperatures. Therefore, the search for an electrolyte which is stable at these temperatures is of utmost importance. Here, such electrolytes are introduced in the form of nonflammable deep eutectic solvents (DESs), consisting of sodium bis(trifluoromethane)sulfonimide (NaTFSI) dissolved in N‐methyl acetamide (NMA). Increasing the NaTFSI concentration replaces NMA—NMA hydrogen bonds with strong ionic interactions between NMA, Na+, and TFSI−. These interactions lower NMA's highest occupied molecular orbital (HOMO) energy level compared with that of TFSI−, leading to an increased anodic stability (up to ≈4.65 V versus Na+/Na). (Na3V2(PO4)2F3/carbon nanotube [CNT])/(Na2+x
Ti4O9/C) full cells show 97.0% capacity retention after 250 cycles at 0.2 C and 55 °C. This is considerably higher than for (Na3V2(PO4)2F3/CNT)/(Na2+x
Ti4O9/C) full cells containing a conventional electrolyte. According to the electrochemical impedance analysis, the improved electrochemical stability is linked to the formation of more robust surface films at the electrode/electrolyte interface. The improved durability and safety highlight that DESs can be viable electrolyte alternatives for sodium‐ion batteries.
Radiative Cooling
In article number http://doi.wiley.com/10.1002/aesr.202100159, Dries De Sloovere, An Hardy, and co‐workers, show that careful investigation and optimization of the coordination structure of deep eutectic solvents allows the preparation of a viable electrolyte alternative for sodium‐ion batteries. The optimized electrolyte is durable and nonflammable, considerably improving the safety of battery operation. Furthermore, it can offer a more durable electrochemical performance compared to conventional electrolytes.
Layered Li-rich/Mn-rich NMC (LMR-NMC) is characterized by high initial specific capacities of more than 250 mAh/g, lower cost due to a lower Co content and higher thermal stability than LiCoO2....
Co-free Li-rich layered oxides are gaining interest as feasible positive electrode materials in lithium-ion batteries (LIBs) in terms of energy density, cost reduction, and alleviating safety concerns. Unfortunately, their commercialization is hindered by severe structural degradation that occurs during electrochemical operation. The study at hand demonstrates advanced structural engineering of a Li-rich Co-free oxide with composition Li 1.1 Ni 0.35 Mn 0.55 O 2 by spray pyrolysis and subsequent calcination of an aqueous precursor, creating a segregated structure of two distinct layered phases with space groups R3̅ m (rhombohedral) and C2/m (monoclinic). This particular structure was investigated with powder neutron diffraction, high-resolution analytical transmission electron microscopy imaging, and electron energy loss spectroscopic characterization. This complex structure contributes to the high electrochemical stability and good rate capability observed for this compound (160 mAh/g at C/3 and 100 mAh/g at 1C) . These results provide new insights into the feasibility of developing and commercializing cobalt-free positive electrode materials for LIBs.
A new benign aqueous route toward bismuth‐containing photoelectrodes is proposed to eliminate the need for harmful organic solvents and/or acids. A CuBi2O4 photocathode is prepared by stabilizing the metal ions through complexation in pH neutral aqueous solutions. Merits of the proposed approach are elemental homogeneity (with unique doping possibilities) and ease of fabrication (e.g., high scalability). The prepared aqueous CuBi2O4 precursor forms a nearly phase‐pure kusachiite crystalline phase free of organics residuals and capable of water reduction due to its sufficiently negatively positioned conduction band at −0.4 V versus RHE. Deposition on fluorine doped tin oxide coated glass (FTO/glass) substrates and thermal treatment leads to uniform but granular films of CuBi2O4 with excellent control over stoichiometry and thickness, owing to the facile and non‐destructive synthesis conditions. Ultimately, the optimized CuBi2O4 photocathodes produce AM1.5G photocurrent densities of up to −1.02 mA cm−2 at 0.4 V versus RHE with H2O2 as an electron scavenger, competing with bare CuBi2O4 prepared through less benign non‐aqueous organic synthesis routes.
Electrochemical energy storage plays a vital role in combating global climate change. Nowadays lithium-ion battery technology remains the most prominent technology for rechargeable batteries. A key performance-limiting factor of lithium-ion batteries is the active material of the positive electrode (cathode). Lithium- and manganese-rich nickel manganese cobalt oxide (LMR-NMC) cathode materials for Li-ion batteries are extensively investigated due to their high specific discharge capacities (>280 mAh/g). However, these materials are prone to severe capacity and voltage fade, which deteriorates the electrochemical performance. Capacity and voltage fade are strongly correlated with the particle morphology and nano- and microstructure of LMR-NMCs. By selecting an adequate synthesis strategy, the particle morphology and structure can be controlled, as such steering the electrochemical properties. In this manuscript we comparatively assessed the morphology and nanostructure of LMR-NMC (Li1.2Ni0.13Mn0.54Co0.13O2) prepared via an environmentally friendly aqueous solution-gel and co-precipitation route, respectively. The solution-gel (SG) synthesized material shows a Ni-enriched spinel-type surface layer at the {200} facets, which, based on our post-mortem high-angle annual dark-field scanning transmission electron microscopy and selected-area electron diffraction analysis, could partly explain the retarded voltage fade compared to the co-precipitation (CP) synthesized material. In addition, deviations in voltage fade and capacity fade (the latter being larger for the SG material) could also be correlated with the different particle morphology obtained for both materials.
Layered Li-rich oxides, demonstrating both cationic and
anionic
redox chemistry being used as positive electrodes for Li-ion batteries,
have raised interest due to their high specific discharge capacities
exceeding 250 mAh/g. However, irreversible structural transformations
triggered by anionic redox chemistry result in pronounced voltage
fade (i.e., lowering the specific energy by a gradual decay of discharge
potential) upon extended galvanostatic cycling. Activating or suppressing
oxygen anionic redox through structural stabilization induced by redox-inactive
cation substitution is a well-known strategy. However, less emphasis
has been put on the correlation between substitution degree and the
activation/suppression of the anionic redox. In this work, Ti4+-substituted Li2MnO3 was synthesized
via a facile solution-gel method. Ti4+ is selected as a
dopant as it contains no partially filled d-orbitals. Our study revealed
that the layered “honeycomb-ordered” C2/m structure is preserved when increasing the Ti
content to x = 0.2 in the Li2Mn1–x
Ti
x
O3 solid
solution, as shown by electron diffraction and aberration-corrected
scanning transmission electron microscopy. Galvanostatic cycling hints
at a delayed oxygen release, due to an improved reversibility of the
anionic redox, during the first 10 charge–discharge cycles
for the x = 0.2 composition compared to the parent
material (x = 0), followed by pronounced oxygen redox
activity afterward. The latter originates from a low activation energy
barrier toward O–O dimer formation and Mn migration in Li2Mn0.8Ti0.2O3, as deduced
from first-principles molecular dynamics (MD) simulations for the
“charged” state. Upon lowering the Ti substitution to x = 0.05, the structural stability was drastically improved
based on our MD analysis, stressing the importance of carefully optimizing
the substitution degree to achieve the best electrochemical performance.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.