Aqueous rechargeable zinc–manganese dioxide batteries show great promise for large‐scale energy storage due to their use of environmentally friendly, abundant, and rechargeable Zn metal anodes and MnO2 cathodes. In the literature various intercalation and conversion reaction mechanisms in MnO2 have been reported, but it is not clear how these mechanisms can be simultaneously manipulated to improve the charge storage and transport properties. A systematical study to understand the charge storage mechanisms in a layered δ‐MnO2 cathode is reported. An electrolyte‐dependent reaction mechanism in δ‐MnO2 is identified. Nondiffusion controlled Zn2+ intercalation in bulky δ‐MnO2 and control of H+ conversion reaction pathways over a wide C‐rate charge–discharge range facilitate high rate performance of the δ‐MnO2 cathode without sacrificing the energy density in optimal electrolytes. The Zn‐δ‐MnO2 system delivers a discharge capacity of 136.9 mAh g−1 at 20 C and capacity retention of 93% over 4000 cycles with this joint charge storage mechanism. This study opens a new gateway for the design of high‐rate electrode materials by manipulating the effective redox reactions in electrode materials for rechargeable batteries.
Porous structured silicon has been regarded as a promising candidate to overcome pulverization of silicon-based anodes. However, poor mechanical strength of these porous particles has limited their volumetric energy density towards practical applications. Here we design and synthesize hierarchical carbon-nanotube@silicon@carbon microspheres with both high porosity and extraordinary mechanical strength (>200 MPa) and a low apparent particle expansion of~40% upon full lithiation. The composite electrodes of carbon-nanotube@silicon@carbon-graphite with a practical loading (3 mAh cm −2) deliver~750 mAh g −1 specific capacity, <20% initial swelling at 100% state-of-charge, and~92% capacity retention over 500 cycles. Calendered electrodes achieve~980 mAh cm −3 volumetric capacity density and <50% end-of-life swell after 120 cycles. Full cells with LiNi 1/3 Mn 1/3 Co 1/3 O 2 cathodes demonstrate >92% capacity retention over 500 cycles. This work is a leap in silicon anode development and provides insights into the design of electrode materials for other batteries.
We demonstrate that the highly active but unstable nanostructured intermediate-temperature solid oxide fuel cell cathode, La0.6Sr0.4CoO3-δ (LSCo), can retain its high oxygen reduction reaction (ORR) activity with exceptional stability for 4000 h at 700 °C by overcoating its surfaces with a conformal layer of nanoscale ZrO2 films through atomic layer deposition (ALD). The benefits from the presence of the nanoscale ALD-ZrO2 overcoats are remarkable: a factor of 19 and 18 reduction in polarization area-specific resistance and degradation rate over the pristine sample, respectively. The unique multifunctionality of the ALD-derived nanoscaled ZrO2 overcoats, that is, possessing porosity for O2 access to LSCo, conducting both electrons and oxide-ions, confining thermal growth of LSCo nanoparticles, and suppressing surface Sr-segregation is deemed the key enabler for the observed stable and active nanostructured cathode.
With advances in porous carbon synthesis techniques, hierarchically porous carbon (HPC) materials are being utilized as relatively new sorbents for CO 2 capture applications. These HPC materials were used as a platform to prepare samples with differing textural properties and morphologies to elucidate structure−property relationships. It was found that high microporous content, rather than overall surface area, was of primary importance for predicting good CO 2 capture performance. Two HPC materials were analyzed, each with near identical high surface area (∼2700 m 2 /g) and colossally high pore volume (∼10 cm 3 /g), but with different microporous content and pore size distributions, which led to dramatically different CO 2 capture performance. Overall, large pore volumes obtained from distinct mesopores were found to significantly impact adsorption performance. From these results, an optimized HPC material was synthesized that achieved a high CO 2 capacity of ∼3.7 mmol/g at 25 °C and 1 bar.
Figure 6 in this manuscript was published without the corresponding equivalent circuit (Figure 6c). The corrected version including Figure 6c is below. CORRECTION Figure 6. Electrochemical impedance spectra at 3.8 V for a) UC and various oxides coated LiMn 2 O 4 with 0 th cycle at room temperature, b) higher frequency (10 MHz to 1Hz) semicircle region, and c) equivalent circuit fi t for the impedance spectra.
We report that the long-term stability of a conventional mixed oxide-ion and electron conducting solid oxide fuel cell cathode, La 0.6 Sr 0.4 Fe 0.8 Co 0.2 O 3−δ -Gd 0.2 Ce 0.8 O 1.9 (LSCF-GDC) composite, can be markedly improved by functionalizing its surfaces with a conformal layer of nanoscale ZrO 2 films through atomic layer deposition (ALD). Over a >1100 h testing at 800 °C, the overcoated LSCF-GDC cathode exhibited respective polarization and ohmic area-specific-resistances 3 and 1.5 times lower than the pristine sample, whereas the pristine LSCF-GDC cathode degraded at a rate 4 times faster than the overcoated one. The multifunctionality of porosity, mixed conductivity, and suppressed Srenrichment enabled by the nanoscaled ALD-ZrO 2 overcoats are attributed to the performance retention observed for the overcoated cathode.
Atomic layer deposition (ALD) has evolved as an important technique to coat conformal protective thin films on cathode and anode particles of lithium ion batteries to enhance their electrochemical performance. Coating a conformal, conductive and optimal ultrathin film on cathode particles has significantly increased the capacity retention and cycle life as demonstrated in our previous work. In this work, we have unearthed the synergetic effect of electrochemically active iron oxide films coating and partial doping of iron on LiMn1.5Ni0.5O4 (LMNO) particles. The ionic Fe penetrates into the lattice structure of LMNO during the ALD process. After the structural defects were saturated, the iron started participating in formation of ultrathin oxide films on LMNO particle surface. Owing to the conductive nature of iron oxide films, with an optimal film thickness of ~0.6 nm, the initial capacity improved by ~25% at room temperature and by ~26% at an elevated temperature of 55 °C at a 1C cycling rate. The synergy of doping of LMNO with iron combined with the conductive and protective nature of the optimal iron oxide film led to a high capacity retention (~93% at room temperature and ~91% at 55 °C) even after 1,000 cycles at a 1C cycling rate.
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