Search

Various properties of sodium ion batteries deteriorate severely when dropping to subzero temperature. Herein, we reveal an accelerated charge-transfer mechanism for high-voltage Na3V2(PO4)2F3 cathode through constructing weakly-solvating architecture, which endows it with superior temperature adaptability (capacity retention of C − 25 ∘ C / C 25 ∘ C reaches 90.8%). The resulting weak solvation effects synergistically lower the activation energy barrier for charge-transfer reactions, thus accelerating the kinetics at low temperature and increasing the energy density by ∼75 Wh Kg−1. Ab initio molecular dynamics calculations show that a weakly-solvating structure forms spontaneously in a low-concentration electrolyte (merely 0.3 M) and thereby facilitates Na+ desolvation process. Besides, visual TOF-SIMS confirms the construction of a dense and uniform cathode/electrolyte interface layer, which optimizes the interface chemistry and improves the interfacial kinetics. In-situ and ex-situ XRD also evidence a smaller degree of structural evolution of the Na3V2(PO4)2F3 cathode, which contributes to long-term durability (attaining a high capacity retention of 93.4% after 1000 cycles at −25 °C). Furthermore, it is demonstrated that under such extreme conditions the Na3V2(PO4)2F3||hard-carbon full cell functions well for over 300 h. These findings elucidate the roles of weak solvation construction in realizing faster kinetics for high-voltage cathodes and provide a feasible pathway for achieving more practical sodium ion batteries.

For sodium-ion batteries (SIBs), the electrochemical process for electrodes involves ion transport in the solid electrolyte interphase (SEI) and active materials. Generally, the large ion radius of Na+ is often considered as the key factor in poor electrode kinetics. However, for conversion-type metal oxide anodes with low redox potentials, unstable SEIs as well as the corresponding kinetic barrier also have significant effects on electrochemical behaviors and deserve more attention. Herein, porous and micro-spherical (Mn0.6Co0.3Ni0.1)3O4 is tailored as a SIB anode using co-precipitation. A high Mn percentage is beneficial to the formation of a micro-spherical morphology during co-precipitation. Due to its lack of electrochemical activity, Mn also contributes to the morphological stability of active materials during cycling. This allows for a clear observation regarding morphological changes of SEI products generated at the electrode surface. It is revealed that branch-like products are gradually converted into a dense interphase layer at electrode surfaces during cycling. The unstable and uneven topography of these electrode surfaces generates kinetic barriers that account for low rate capacities of the as-obtained (Mn0.6Co0.3Ni0.1)3O4 materials. The synthesized metal oxide is able to retain 98.1% of its initial sodiation capacity after 2000 cycles at 0.5 A g−1.

Existing rechargeable batteries not only fail to meet the demand for high power applications but also cause heavy metal pollution. Li-ion capacitors (LICs), which can achieve higher charging speeds and energy densities than supercapacitors, have attracted extensive attention. Nevertheless, sluggish Li-ion diffusion of the battery-type anode results in limited rate performance of LICs. Herein, high-performance LICs using by both battery and capacitor type Mn2V2O7-graphene (MVO-G) anodes and hempstem-derivated activated carbon (HSAC) cathodes with a large surface area are first reported. In addition to high pseudocapacitance, the MVO-G possesses the advantage of fast Li+ storage performance making it a suitable choice for advanced LIC anodes. Graphene is employed to enhance overall conductivity and cycling stability leading to enhanced energy storage. The MVO-G//HSAC LICs exhibit a high energy density of 148.1 Wh kg–1 at a power density of 150 W kg–1 and 25 Wh kg–1 even at 15 kW kg–1. More importantly, the MVO-G//HSAC LICs also show excellent cycling stability of 90% after 15000 cycles, which is expected for high performance energy storage systems.

Sluggish kinetics and limited reversible capacity present two major challenges for layered titanates to achieve satisfactory sodium-ion storage performance at subzero-temperatures (subzero-T). To f...

An ultra-high ion-selective Nafion composite membrane modified by phosphotungstic acid (PWA) coupled silica for vanadium redox flow battery (VRB) was constructed and prepared through solution casting. The composite membrane exhibits excellent proton conductivity and vanadium ions blocking property by incorporating the nanohybrid composed of silica and PWA into the Nafion ionomer. Simple tuning for the filling amount of the nanohybrid endows the obtained membranes preeminent vanadium barrier property including a minimum vanadium permeability of 3.13 × 10−7 cm2 min−1 and a maximum proton conductivity of 0.081 S cm−1 at 25 °C. These indicate an ion selectivity of 2.59 × 105 S min cm−3, which is 6.8 times higher than that of recast Nafion (0.33 × 105 S min cm−3). As a result, the VRB with the composite membrane shows superior battery performance containing a lower self-discharge rate, higher capacity retention and more robust cyclic stability compared with recast Nafion over a range of current densities from 40 to 100 mA cm−2.

The catalyst in the oxygen electrode is the core component of the aqueous metal-air battery, which plays a vital role in the determination of the open circuit potential, energy density, and cycle life of the battery. For rechargeable aqueous metal-air batteries, the catalyst should have both good oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic performance. Compared with precious metal catalysts, non-precious metal materials have more advantages in terms of abundant resource reserves and low prices. Over the past few years, great efforts have been made in the development of non-precious metal bifunctional catalysts. This review selectively evaluates the advantages, disadvantages and development status of recent advanced materials including pure carbon materials, carbon-based metal materials and carbon-free materials as bifunctional oxygen catalysts. Preliminary improvement strategies are formulated to make up for the deficiency of each material. The development prospects and challenges facing bifunctional catalysts in the future are also discussed.

Non-noble metal materials are regarded as the most promising catalysts for the oxygen reduction reaction (ORR) to overcome the inherent defects of Pt-based catalysts, like high cost, limited availability and insufficient stability. Here, we fabricate sandwich-like Co encapsulated nitrogen doped carbon polyhedron/graphene (s-Co@NCP/rGO) via a facile and scalable strategy by loading Co-based zeolitic imidazolate framework (ZIF-67) and graphene oxide (GO) layers individually on a polyurethane (PU) sponge template. The 3D sandwich structure is maintained with the assistance of the sponge template, which promotes the uniform dispersion of ZIF-67-derived Co embedded nitrogen doped carbon polyhedra (Co@NCP) and prevents the graphene plates from agglomerating during the annealing process. The final product demonstrates considerable catalytic performance for the ORR with a half-wave potential of 0.85 V, preferable stability and increased poisoning tolerance by comparison to 20 wt% Pt/C, which stems from the 3D sandwich-like structure, N/Co-doping effect, large accessible surface area and hierarchical porous structures. The excellent ORR performance of the catalysts means that they can be utilised in a Zn-air battery as cathode catalysts. During such a demonstration, s-Co@NCP/rGO shows a high open-circuit voltage of 1.466 V, remarkable long-term durability and an outstanding peak power density of 186 mV cm-2, which shows its high potential as a prospective alternative for widespread practical application in the field of non-noble metal ORR catalysts.

Different calcination atmospheres of air, 50% oxygen (vs. N2) and pure oxygen have been used to prepare special LiNi0.8Co0.1Mn0.1O2 cathode materials to observe the influence of oxygen composition. To investigate the structure and electrochemical property of the samples using different oxygen compositions, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), cycling performance tests and electrochemical impedance spectroscopy (EIS) were carried out. XRD, SEM, and XPS results show that the sample made using higher oxygen composition has less cation mixing and lower levels of Ni2+. However, both samples have almost the same oxygen environments on their surfaces as well as micro-morphology and size. The sample with a higher oxygen composition shows better electrochemical performance. Interestingly, the electrochemical performance of the sample made using 50% oxygen is similar to that made with pure oxygen and much better than the sample made with air. It has a specific capacity of 202.4 mAh g−1 at 0.1C and a capacity retention of 85.2% after 300 cycles at 1C, which may be meaningful for balancing cost and performance.

One of the main issues for titanium-based anode materials is their poor electronic conductivity and this issue can affect their rate performance. For conquering this drawback, many approaches have been proposed. In this report, SrLi2Ti6O14 as one of the titanium-based anode materials is prepared via a facile sol–gel method and subsequently it has been composited with silver to elevate its electronic conductivity. Upon the analysis of electrochemical results, the SrLi2Ti6O14/Ag composite with 6 wt% Ag can deliver an initial capacity of 164.9 mAh g−1. After 50 cycles, the sample can still retain 154.6 mAh g−1 with 93.8% retention of the first cycle. Meanwhile, the SrLi2Ti6O14/Ag composite with 6 wt% Ag can also exhibit good rate capacities, even at 300 mA g−1, its capacity can be firmly kept at 140.0 mAh g−1. In addition, in situ X-ray diffraction characterization shows the structural reversibility of the SrLi2Ti6O14/Ag composite with 6 wt% Ag during cycling. All the electrochemical results indicate that the SrLi2Ti6O14/Ag composite with 6 wt% Ag can be a promising anode material for lithium ion batteries.

A highly proton-/vanadium-selective perfluorosulfonic acid (Nafion) membrane modified by phosphotungstic acid (PWA)-anchored nano Kevlar fibers (NKFs) and nano silica particles (NSP) for a vanadium redox flow battery (VRB) was fabricated through solution casting. The nanohybrid composed of NKFs, NSP and PWA exhibited excellent compatibility with the polymer matrix, and effectively suppressed the vanadium ion crossover. In addition, the anchoring of PWA was of great significance for maintaining the ion exchange capacity and constructing continuous proton transport channels. The optimal Nafion-(NKFs@NSP/PWA) membrane presented a high proton conductivity (0.079 S cm−1) and a low vanadium permeability (6.27 × 10−7 cm2 min−1), resulting in an ion selectivity of 1.26 × 105 S min cm−3, which is much higher than that of recast Nafion (0.34 × 105 S min cm−3). Moreover, the VRB assembled with the modified membrane showed a lower self-discharge rate, higher battery efficiency and superior capacity retention than that with the recast Nafion over a range of current densities from 40 mA cm−2 to 100 mA cm−2.

Sluggish kinetics and limited reversible capacity present two major challenges for layered titanates to achieve satisfactory sodium-ion storage performance at subzero-temperatures (subzero-T). To facilitate sodiation dynamics and improve reversible capacity, we proposed an additive-free anode with Sn(II) located between layers. Sn-5s in interlayer-confining Sn(II), which has a larger negative charge, will hybridize with O-2p to trigger charge redistribution, thereby enhancing electronic conductivity. H-titanates with an open framework are designed to stabilize Sn(II) and restrain subsequent volume expansion, which could potentially surpass the capacity limitation of titanate-based materials via a joint alloying-intercalation reaction with high reversibility. Moreover, the generation of conductive Na