Promoting Surface Electric Conductivity for High-Rate LiCoO2.

The cathode materials work as the host framework for both Li+ diffusion and electron transport in Li-ion batteries. The Li+ diffusion property is always the research focus, while the electron transport property is less studied. Herein, we propose a unique strategy to elevate the rate performance through promoting the surface electric conductivity. Specifically, a disordered rock-salt phase was coherently constructed at the surface of LiCoO2 , promoting the surface electric conductivity by over one magnitude. It increased the effective voltage (Veff ) imposed in the bulk, thus driving more Li+ extraction/insertion and making LiCoO2 exhibit superior rate capability (154 mAh g-1 at 10 C), and excellent cycling performance (93 % after 1000 cycles at 10 C). The universality of this strategy was confirmed by another surface design and a simulation. Our findings provide a new angle for developing high-rate cathode materials by tuning the surface electron transport property.

Densification of Cathode/Electrolyte Interphase to Enhance Reversibility of LiCoO2 at 4.65 V.

For LiCoO2 (LCO) operated beyond 4.55 V (vs Li/Li+), it usually suffers from severe surface degradation. Constructing a robust cathode/electrolyte interphase (CEI) is effective to alleviate the above issues, however, the correlated mechanisms still remain vague. Herein, a progressively reinforced CEI is realized via constructing Zr─O deposits (ZrO2 and Li2ZrO3) on LCO surface (i.e., Z-LCO). Upon cycle, these Zr─O deposits can promote the decomposition of LiPF6, and progressively convert to the highly dispersed Zr─O─F species. In particular, the chemical reaction between LiF and Zr─O─F species further leads to the densification of CEI, which greatly reinforces its toughness and conductivity. Combining the robust CEI and thin surface rock-salt layer of Z-LCO, several benefits are achieved, including stabilizing the surface lattice oxygen, facilitating the interface Li+ transport kinetics, and enhancing the reversibility of O3/H1-3 phase transition, etc. As a result, the Z-LCO||Li cells exhibit a high capacity retention of 84.2% after 1000 cycles in 3-4.65 V, 80.9% after 1500 cycles in 3-4.6 V, and a high rate capacity of 160 mAh g-1 at 16 C (1 C = 200 mA g-1). This work provides a new insight for developing advanced LCO cathodes.

Sequential co-reduction of nitrate and carbon dioxide enables selective urea electrosynthesis.

Despite the recent achievements in urea electrosynthesis from co-reduction of nitrogen wastes (such as NO3-) and CO2, the product selectivity remains fairly mediocre due to the competing nature of the two parallel reduction reactions. Here we report a catalyst design that affords high selectivity to urea by sequentially reducing NO3- and CO2 at a dynamic catalytic centre, which not only alleviates the competition issue but also facilitates C-N coupling. We exemplify this strategy on a nitrogen-doped carbon catalyst, where a spontaneous switch between NO3- and CO2 reduction paths is enabled by reversible hydrogenation on the nitrogen functional groups. A high urea yield rate of 596.1 µg mg-1 h-1 with a promising Faradaic efficiency of 62% is obtained. These findings, rationalized by in situ spectroscopic techniques and theoretical calculations, are rooted in the proton-involved dynamic catalyst evolution that mitigates overwhelming reduction of reactants and thereby minimizes the formation of side products.

Revealing the Grain-Boundary-Cracking Induced Capacity Decay of a High-Voltage LiCoO2 at 4.6 V.

During a practical battery manufacture process, the LiCoO2 (LCO) electrodes are usually rolled with high pressure to achieve better performance, including reducing electrode polarization, increasing compact density, enhancing mechanical toughness, etc. In this work, a high-voltage LCO (HV-LCO) is achieved via modulating a commercialized LCO with an Al/F enriched and spinel reinforced surface structure. We reveal that the rolling can more or less introduce risk of grain-boundary-cracking (GBC) inside the HV-LCO and accelerate the capacity decay when cycled at 3-4.6 V vs Li/Li+. In particular, the concept of interface structure is proposed to explain the reason for the deteriorated cycle stability. As the GBC is generated, the interface structure of HV-LCO alters from a surface spinel phase to a hybrid of surface spinel plus boundary layer phases, leading to the exposure of some the nonprotective layer phase against the electrolyte. This alternation causes serious bulk structure damage upon cycles, including expanding GBC among the primary crystals, forming intragranular cracks and inactive spinel phases inside the bulk regions, etc., eventually leading to the deteriorated cycle stability. Above all, we realize that it is far from enough to achieve a eligible high-voltage LCO via only applying surface modification. This work provides a new insight for developing more advanced LCO cathodes.

Structure evolution and energy storage mechanism of Zn3V3O8 spinel in aqueous zinc batteries.

Spinel-type materials are promising for the cathodes in rechargeable aqueous zinc batteries. Herein, Zn3V3O8 is synthesized via a simple solid-state reaction method. By tuning the Zn(CF3SO3)2 concentration in electrolytes and the cell voltage ranges, improved electrochemical performance of Zn3V3O8 can be achieved. The optimized test conditions give rise to progressive structure evolution from bulk to nano-crystalline spinel, which leads to capacity activation in the first few cycles and stable cycling performance afterward. Furthermore, the energy storage mechanism in this nano-crystalline spinel is interpreted as the co-intercalation of zinc ions and protons with some water. This work provides a new viewpoint of the structure evolution and correlated energy storage mechanism in spinel-type host materials, which would benefit the design and development of next-generation batteries.

Oxygen-Deficient ß-MnO2@Graphene Oxide Cathode for High-Rate and Long-Life Aqueous Zinc Ion Batteries.

Recent years have witnessed a booming interest in grid-scale electrochemical energy storage, where much attention has been paid to the aqueous zinc ion batteries (AZIBs). Among various cathode materials for AZIBs, manganese oxides have risen to prominence due to their high energy density and low cost. However, sluggish reaction kinetics and poor cycling stability dictate against their practical application. Herein, we demonstrate the combined use of defect engineering and interfacial optimization that can simultaneously promote rate capability and cycling stability of MnO2 cathodes. ß-MnO2 with abundant oxygen vacancies (VO) and graphene oxide (GO) wrapping is synthesized, in which VO in the bulk accelerate the charge/discharge kinetics while GO on the surfaces inhibits the Mn dissolution. This electrode shows a sustained reversible capacity of ~ 129.6 mAh g-1 even after 2000 cycles at a current rate of 4C, outperforming the state-of-the-art MnO2-based cathodes. The superior performance can be rationalized by the direct interaction between surface VO and the GO coating layer, as well as the regulation of structural evolution of ß-MnO2 during cycling. The combinatorial design scheme in this work offers a practical pathway for obtaining high-rate and long-life cathodes for AZIBs.

Highly crystalline nickel hexacyanoferrate as a long-life cathode material for sodium-ion batteries.

Prussian blue analogs (PBAs) are attractive cathode candidates for high energy density, including long life-cycle rechargeable batteries, due to their non-toxicity, facile synthesis techniques and low cost. Nevertheless, traditionally synthesized PBAs tend to have a flawed crystal structure with a large amount of [Fe(CN)6]4- openings and the presence of crystal water in the framework; therefore the specific capacity achieved has continuously been low with poor cycling stability. Herein, we demonstrate low-defect and sodium-enriched nickel hexacyanoferrate nanocrystals synthesized by a facile low-speed co-precipitation technique assisted by a chelating agent to overcome these problems. As a consequence, the prepared high-quality nickel hexacyanoferrate (HQ-NiHCF) exhibited a high specific capacity of 80 mA h g-1 at 15 mA g-1 (with a theoretical capacity of ∼85 mA h g-1), maintaining a notable cycling stability (78 mA h g-1 at 170 mA g-1 current density) without noticeable fading in capacity retention after 1200 cycles. This low-speed synthesis strategy for PBA-based electrode materials could be also extended to other energy storage materials to fabricate high-performance rechargeable batteries.