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At least 1,297 records · Page 72

High rate sodium ion battery anodes from block copolymer templated mesoporous nickel–cobalt carbonates and oxides

In this work, micelle-templated ordered mesoporous nickel–cobalt carbonates and oxides are fabricated using a metal nitrate–citric acid strategy, which avoids the hydrolysis and aging requirements associated with sol–gel chemistry. A series of mesoporous Ni x Co (3– x ) (CO 3 ) y and Ni x Co (3– x ) O 4 films with varying Ni–Co compositions and 14 ± 4 nm mesopores are fabricated with the same block copolymer template. AFM and GISAXS analysis indicates that the mesostructure is maintained through the formation of the carbonate and oxide, while GIXD profiles confirm formation of pure spinel phases of semi-crystalline Ni x Co (3– x ) O 4 . The micelle templated mesopores are interconnected and provide transport paths for the electrolyte to minimize the solid-state diffusion requirements associated with battery electrodes. These materials exhibit good performance as sodium ion battery anodes even at high current densities of 4 A g –1 . Amongst the mixed-metal oxides, Ni 2 CoO 4 exhibits the highest specific capacity of 239 mA h g –1 after galvanostatic cycling at a current density of 1 A g –1 for 10 cycles. We attribute the superior performance of Ni 2 CoO 4 at high rates to the high surface area and short ion-diffusion paths of the nanoporous anode architecture, while the higher nickel content in the mixed metal oxide provides enhanced stability during oxide formation along with enhanced electronic conductivity, leading to improved cycling stability of the anode. This micelle template metal nitrate–citric acid method enables new possibilities for fabricating variety of ordered mesoporous mixed-metal carbonates and oxides that could be used in a wide range of applications.

25 ENERGY STORAGE↗

Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review

Unlike the revolutionary advances in the anodes of lithium-ion batteries from Li intercalation materials to Li alloy and/or conversion reaction materials, the development of the cathode is still dominated by the Li intercalation compounds. Transition metal ions are essential in these cathodes as the rapid redox reaction centers, and one of the biggest challenges for the TM-based cathodes is the capacity and power fading especially at an elevated temperature, which is directly associated with the dissolution–migration–deposition (DMD) process of TMs from the cathode materials. This process not only alters the surface structure of the cathode materials, but more importantly, changes the SEI composition at the anode side. There is no doubt that the TM-DMD issue should be addressed thoroughly to unlock the potential of these compounds to enable a prolonged battery lifetime. This review article mainly focuses on research activities with regard to the DMD process in TM-based cathode materials. In the first four sections, we choose Mn-based cathodes as an example to discuss how Mn DMD relates to the capacity fade of the cell, and what possible approaches might suppress the DMD process by modification of the electrode or electrolyte. In the fifth section, we discuss the TM DMD process in Ni-, Co-, Fe- and V-containing cathode materials. Furthermore, this article reviews the frontier electrochemical research on TM-based cathodes and summarizes the progress and challenges, thereby helping to advance future R&D of LIBs.

25 ENERGY STORAGE↗

Monitoring solvent dynamics and ion associations in the formation of cubic octamer polyanion in tetramethylammonium silicate solutions

NMR methods were utilized to monitor the in situ structural and dynamic changes of various species in highly alkaline tetramethylammonium (TMA) silicate solutions. Quantitative 29Si NMR, 1H, 2H, and 17O relaxation NMR, and 1H and 29Si diffusion NMR of silicates, TMA, H2O and D2O demonstrate that the growth of the cubic octamer Q38 is accompanied by reduced water mobility and increasing TMA coordination number per Q38, which reaches an equilibrium value of 4.5 at 15 °C. Temperature-dependent measurements further reveal that the increased control over speciation by TMA at lower temperatures results from the more stable ion associations via slower solvent motions.

Chen, Ying↗

Pursuing graphite-based K-ion O 2 batteries: a lesson from Li-ion batteries

The replacement of lithium metal by lithium intercalated graphite was crucial for developing safe lithium-ion batteries. Superoxide-based potassium–oxygen batteries represent an exciting metal–oxygen battery with the highest energy efficiencies. However, using potassium metal is a more serious safety threat than lithium. Herein, we explore the possibility of graphite-intercalation anodes for potassium-ion oxygen batteries (PIOBs) with enhanced safety. This work demonstrates for the first time that establishing an artificial potassium salt-rich solid electrolyte interphase (SEI) enables a reversible graphite-intercalation anode (249.6 mA h g -1 after 600 cycles) in a potassium bis(trifluoromethanesulfonyl)imide (KTFSI)-based localized high-concentration electrolyte. Such an electrolyte is stable with the superoxide cathode. The PIOB delivers energy efficiencies above 90% at a depth of discharge (DOD) of 25% for 80 cycles. A three-electrode measurement shows that its overpotential mainly comes from the anode. The lifespan is limited to the gradual degradation of the artificial SEI caused by oxygen crossover. This work represents a step towards achieving holistic anode–electrolyte–cathode compatibility in a PIOB and its realistic evaluation under a controlled DOD.

25 ENERGY STORAGE↗

A single-ion-conducting polymer and high-entropy Li-garnet composite electrolyte with simultaneous enhancement in ion transport and mechanical properties

Enabling the lithium metal anode has been the holy grail for improving the energy density for the next generation advanced batteries. Developing electrolytes that will suppress Li dendrite growth and provide sufficient ionic conductivity remains a major challenge in this field. In this study, we develop a polymer–ceramic composite electrolyte for lithium metal batteries. The polymer matrix is a vinyl ethylene carbonate (VEC) based single-ion-conducting polymer electrolyte. The ceramic filler is a Li 7 La 3 Zr 0.5 Nb 0.5 Ta 0.5 Hf 0.5 O 12 high-entropy Li-garnet (HE Li-garnet) ceramic, which is less prone to surface Li 2 CO 3 formation compared to Al-doped Li garnets. The addition of HE Li-garnet leads to a 7-fold increase in the ionic conductivity (8.6 × 10 −5 S cm −1 at 30 °C) compared to the pure polymer, while maintaining a high Li + transference of 0.73. Proton nuclear magnetic resonance and thermogravimetric analysis results suggest that the addition of HE Li-garnet results in a lower degree of polymerization of VEC, leaving more unpolymerized VEC monomers in the matrix, serving as the governing mechanism for conductivity enhancement. The favorable interactions between HE Li-garnet particles and the polymer matrix lead to a stable and well-mixed composite with 2-fold enhancement of storage modulus at 40 °C. The simultaneous ion transport and mechanical property enhancement significantly improves the composite electrolyte's dendrite resistance and cycle life in Li symmetric cells. This work highlights the positive role HE Li-garnet can play in improving polymer electrolytes to enable lithium metal anodes.

Ock, Ji-young [Oak Ridge National Laboratory (ORNL↗

Cancellation of the ion deflection due to electron-suppression magnetic field in a negative-ion accelerator

A new magnetic configuration is proposed for the suppression of co-extracted electrons in a negative-ion accelerator. This configuration is produced by an arrangement of permanent magnets embedded in one accelerator grid and creates an asymmetric local magnetic field on the upstream and downstream sides of this grid. Thanks to the “concentration” of the magnetic field on the upstream side of the grid, the resulting deflection of the ions due to magnetic field can be “intrinsically” cancelled by calibrating the configuration of permanent magnets. At the same time, the suppression of co-extracted electrons can be improved.

43 PARTICLE ACCELERATORS↗