Manipulating OH- -Mediated Anode-Cathode Cross-Communication Toward Long-Life Aqueous Zinc-Vanadium Batteries.

The anode-cathode interplay is an important but rarely considered factor that initiates the degradation of aqueous zinc ion batteries (AZIBs). Herein, to address the limited cyclability issue of V-based AZIBs, Al2 (SO4 )3 is proposed as decent electrolyte additive to manipulate OH- -mediated cross-communication between Zn anode and NaV3 O8 ⋅ 1.5H2 O (NVO) cathode. The hydrolysis of Al3+ creates a pH≈0.9 strong acidic environment, which unexpectedly prolongs the anode lifespan from 200 to 1000 h. Such impressive improvement is assigned to the alleviation of interfacial OH- accumulation by Al3+ adsorption and solid electrolyte interphase formation. Accordingly, the strongly acidified electrolyte, associated with the sedated crossover of anodic OH- toward NVO, remarkably mitigate its undesired dissolution and phase transition. The interrupted OH- -mediated communication between the two electrodes endows Zn||NVO batteries with superb cycling stability, at both low and high scan rates.

Phosphorus-Doping-Induced Surface Vacancies of 3D Na2 Ti3 O7 Nanowire Arrays Enabling High-Rate and Long-Life Sodium Storage.

Sodium-ion batteries have attracted interest as an alternative to lithium-ion batteries because of the abundance and cost effectiveness of sodium. However, suitable anode materials with high-rate and stable cycling performance are still needed to promote their practical application. Herein, three-dimensional Na2 Ti3 O7 nanowire arrays with enriched surface vacancies endowed by phosphorus doping are reported. As anodes for sodium-ion batteries, they deliver a high specific capacity of 290 mA h g-1 at 0.2 C, good rate capability (50 mA h g-1 at 20 C), and stable cycling capability (98 % capacity retention over 3100 cycles at 20 C). The superior electrochemical performance is attributed to the synergistic effects of the nanowire arrays and phosphorus doping. The rational structure can provide convenient channels to facilitate ion/electron transport and improve the capacitive contributions. Moreover, the phosphorus-doping-induced surface vacancies not only provide more active sites but also improve the intrinsic electrical conductivity of Na2 Ti3 O7 , which will enable electrode materials with excellent sodium storage performance. This work may provide an effective strategy for the synthesis of other anode materials with fast electrochemical reaction kinetics and good sodium storage performance.

Hierarchical GeP5/Carbon Nanocomposite with Dual-Carbon Conductive Network as Promising Anode Material for Sodium-Ion Batteries.

Due to the Earth's scarcity of lithium, replacing lithium with earth-abundant and low-cost sodium for sodium-ion batteries (SIBs) has recently become a promising substitute for lithium-ion batteries. However, the shortage of appropriate anode materials limits the development of SIBs. Here, a dual-carbon conductive network enhanced GeP5 (GeP5/acetylene black/partially reduced graphene oxide sheets (GeP5/AB/p-rGO)) composite is successfully prepared by a facile ball milling method. The dual-carbon network not only provides more transport pathways for electrons but also relaxes the huge volume change of the electrode material during the charge/discharge process. Compared with only AB- or GO-modified GeP5 (GeP5/AB or GeP5/GO) composite, the GeP5/AB/p-rGO composite shows a superior sodium storage performance with an excellent rate and cycle performance. It delivers a high reversible capacity of 597.5 and 175 mAh/g at the current density of 0.1 and 5.0 A/g, respectively. Furthermore, at the current density of 0.5 A/g, the GeP5/AB/p-rGO composite shows the reversible capacity of 400 mAh/g after 50 cycles with a little capacity attenuation. All above results prove that the GeP5/AB/p-rGO composite has a good prospect of application as an anode material for SIBs.

In Situ Encapsulating α-MnS into N,S-Codoped Nanotube-Like Carbon as Advanced Anode Material: α → ß Phase Transition Promoted Cycling Stability and Superior Li/Na-Storage Performance in Half/Full Cells.

Incorporation of N,S-codoped nanotube-like carbon (N,S-NTC) can endow electrode materials with superior electrochemical properties owing to the unique nanoarchitecture and improved kinetics. Herein, α-MnS nanoparticles (NPs) are in situ encapsulated into N,S-NTC, preparing an advanced anode material (α-MnS@N,S-NTC) for lithium-ion/sodium-ion batteries (LIBs/SIBs). It is for the first time revealed that electrochemical α → ß phase transition of MnS NPs during the 1st cycle effectively promotes Li-storage properties, which is deduced by the studies of ex situ X-ray diffraction/high-resolution transmission electron microscopy and electrode kinetics. As a result, the optimized α-MnS@N,S-NTC electrode delivers a high Li-storage capacity (1415 mA h g-1 at 50 mA g-1 ), excellent rate capability (430 mA h g-1 at 10 A g-1 ), and long-term cycling stability (no obvious capacity decay over 5000 cycles at 1 A g-1 ) with retained morphology. In addition, the N,S-NTC-based encapsulation plays the key roles on enhancing the electrochemical properties due to its high conductivity and unique 1D nanoarchitecture with excellent protective effects to active MnS NPs. Furthermore, α-MnS@N,S-NTC also delivers high Na-storage capacity (536 mA h g-1 at 50 mA g-1 ) without the occurrence of such α → ß phase transition and excellent full-cell performances as coupling with commercial LiFePO4 and LiNi0.6 Co0.2 Mn0.2 O2 cathodes in LIBs as well as Na3 V2 (PO4 )2 O2 F cathode in SIBs.

Flexible P-Doped Carbon Cloth: Vacuum-Sealed Preparation and Enhanced Na-Storage Properties as Binder-Free Anode for Sodium Ion Batteries.

In this work, a flexible and self-supporting P-doped carbon cloth (FPCC), which is composed of interwoven mesh of hollow microtubules with porous carbon walls, is prepared via a vacuum-sealed doping technology by employing the commercially available cotton cloth as sustainable and scalable raw material. When directly used as binder-free anode for sodium-ion batteries, the as-prepared FPCC delivers superior Na-storage properties in terms of specific capacity up to 242.4 mA h g-1, high initial Coulombic efficiency of ∼72%, excellent rate capabilities (e.g., 123.1 mA h g-1 at a high current of 1 A g-1), and long-term cycle life (e.g., ∼88% capacity retention after even 600 cycles). All these electrochemical data are better than the undoped carbon cloth control, demonstrating the significance of P-doping to enhance the Na-storage properties of cotton-derived carbon anode. Furthermore, the technologies of electrochemical impedance spectroscopy and galvanostatic intermittent titration technique are implemented to disclose the decrease of charge transfer resistance and improvement of Na-migration kinetics, respectively.