Enhanced mechanical strength of a highly de-lithiated single-crystal Ni-rich cathode to suppress irreversible planar gliding.

The mechanical properties of de-lithiated single-crystal Ni-rich cathodes are causing extensive concern. Here, we first show that the compression hardness of single crystal Ni-rich cathode particles decreases significantly at highly de-lithiated states by micro-compression testing. Thus, phase-boundary hardening was introduced to inhibit the planar gliding, resulting in excellent electrochemical performance.

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.

Synergistic activation of anionic redox via cosubstitution to construct high-capacity layered oxide cathode materials for sodium-ion batteries.

As a potential substitute for lithium-ion battery, sodium-ion batteries (SIBs) have attracted a tremendous amount of attention due to their advantages in terms of cost, safety and sustainability. Nevertheless, further improvement of the energy density of cathode materials in SIBs remains challenging and requires the activation of anion redox reaction (ARR) activity to provide additional capacity. Herein, we report a high-performance Mn-based sodium oxide cathode material, Na0.67Mg0.1Zn0.1Mn0.8O2 (NMZMO), with synergistic activation of ARR by cosubstitution. This material can deliver an ultra-high capacity of âˆ¼233 mAh/g at 0.1 C, which is significantly higher than their single-cation-substituted counterparts and among the best in as-reported MgMn or ZnMn-based cathodes. Various spectroscopic techniques were comprehensively employed and it was demonstrated that the higher capacity of NMZMO originated from the enhanced ARR activity. Neutron pair distribution function and resonant inelastic X-ray scattering experiments revealed that out-of-plane migration of Mg/Zn occurred upon charging and oxygen anions in the form of molecular O2 were trapped in vacancy clusters in the fully-charged-state. In NMZMO, Mg and Zn mutually interacted with each other to migrate toward tetrahedral sites, which provided a prerequisite for further ARR activity enhancement to form more trapped molecular O2. These findings provide unique insight into the ARR mechanism and can guide the development of high-performance cathode materials through ARR enhancement strategies.

Origin of structural degradation in Li-rich layered oxide cathode.

Li- and Mn-rich (LMR) cathode materials that utilize both cation and anion redox can yield substantial increases in battery energy density1-3. However, although voltage decay issues cause continuous energy loss and impede commercialization, the prerequisite driving force for this phenomenon remains a mystery3-6 Here, with in situ nanoscale sensitive coherent X-ray diffraction imaging techniques, we reveal that nanostrain and lattice displacement accumulate continuously during operation of the cell. Evidence shows that this effect is the driving force for both structure degradation and oxygen loss, which trigger the well-known rapid voltage decay in LMR cathodes. By carrying out micro- to macro-length characterizations that span atomic structure, the primary particle, multiparticle and electrode levels, we demonstrate that the heterogeneous nature of LMR cathodes inevitably causes pernicious phase displacement/strain, which cannot be eliminated by conventional doping or coating methods. We therefore propose mesostructural design as a strategy to mitigate lattice displacement and inhomogeneous electrochemical/structural evolutions, thereby achieving stable voltage and capacity profiles. These findings highlight the significance of lattice strain/displacement in causing voltage decay and will inspire a wave of efforts to unlock the potential of the broad-scale commercialization of LMR cathode materials.

Heavy Fluorination via Ion Exchange Achieves High-Performance Li-Mn-O-F Layered Cathode for Li-Ion Batteries.

Lithium-excess manganese layered oxide Li2 MnO3 , attracts much attention as a cathode in Li-ion batteries, due to the low cost and the ultrahigh theoretical capacity (≈460 mA h g-1 ). However, it delivers a low reversible practical capacity (<200 mA h g-1 ) due to the irreversible oxygen redox at high potentials (>4.5 V). Herein, heavy fluorination (9.5%) is successfully implemented in the layered anionic framework of a Li-Mn-O-F (LMOF) cathode through a unique ion-exchange route. F substitution with O stabilizes the layered anionic framework, completely inhibits the O2 evolution during the first cycle, and greatly enhances the reversibility of oxygen redox, delivering an ultrahigh reversible capacity of 389 mA h g-1 , which is 85% of the theoretical capacity of Li2 MnO3 . Moreover, it also induces a thin spinel shell coherently forming on the particle surface, which greatly improves the surface structure stability, making LMOF exhibit a superior cycling stability (a capacity retention of 91.8% after 120 cycles at 50 mA g-1 ) and excellent rate capability. These findings stress the importance of stabilizing the anionic framework in developing high-performance low-cost cathodes for next-generation Li-ion batteries.

Impact of Electrolyte Salts on Na Storage Performance for High-Surface-Area Carbon Anodes.

High-surface-area carbon (HSAC) has been regarded as one of the most promising anode materials for sodium-ion batteries. However, it generally suffers from low initial Coulombic efficiency (ICE), which is closely related to the formation process of a solid electrolyte interface (SEI). Herein, the impact of different electrolyte salts on the electrochemical performance and SEI formation of a commercial HSAC anode is studied. It is found that the use of NaCF3SO3 enables much higher ICE (69.28%) and reversible capacity (283 mA h g-1) of the HSAC anode compared with the NaPF6 electrolyte (59.65%, 243 mA h g-1). Through comprehensive characterizations, the improvement in electrochemical performance facilitated by NaCF3SO3 could be attributed to the reduced amount of NaxC and the thinner SEI formed on the surface of HSAC during the initial cycle, which not only provides extra active sites for Na+ storage but also contributes to the promoted ICE. This work not only provides a deeper understanding of the role of electrolyte salt in SEI formation in the HSAC anode but also proposes a new method to further promote the ICE of the HSAC anode in sodium-ion batteries.

Yeast encapsulation in nanofiber via electrospinning: Shape transformation, cell activity and immobilized efficiency.

To realize encapsulation of living microbial cells and easily evaluation of cell viability after immobilization, the yeast cells were encapsulated in water soluble PAAm nanofiber by a facile and effective electrospinning technology. Firstly, the conductivity, shear viscosity and surface tension of PAAm/yeast electrospinning solution as a function of mass ratios of yeast/PAAm were investigated to determine the optimum solution condition for electrospinning immobilization. After electrospinning, it is interesting to note that the original ellipsoidal structure of yeast cells turns to oblate spheroid structure. To distinguish immobilization structure from the bead appearing during general electrospinning process, immobilization structure and bead structure were compared and analyzed by FESEM and EDX. Free cell activity, the immediate cell activity after electrospinning and cell activity for seven days storage after immobilization were evaluated by dying methods of CTC and methylene blue, respectively. The results show that encapsulation efficiency maintained at about 40%, and immobilized yeast cells remain active even after seven days storage, which provides a promising application prospect for electrospinning immobilization.