Project description:Aqueous graphite-based dual ion batteries have unique superiorities in stationary energy storage systems due to their non-transition metal configuration and safety properties. However, there is an absence of thorough study of the interactions between anions and water molecules and between anions and electrode materials, which is essential to achieve high output voltage. Here we reveal the four-stage intercalation process and energy conversion in a graphite cathode of anions with different configurations. The difference between the intercalation energy and hydration energy of bis(trifluoromethane)sulfonimide makes the best use of the electrochemical stability window of its electrolyte and delivers a high intercalation potential, while BF4- and CF3SO3- do not exhibit a satisfactory potential because the graphite intercalation potential of BF4- is inferior and the graphite intercalation potential of CF3SO3- exceeds the voltage window of its electrolyte. An aqueous dual ion battery based on the intercalation behaviors of bis(trifluoromethane)sulfonimide anions into a graphite cathode exhibits a high voltage of 2.2 V together with a specific energy of 242.74 Wh kg-1. This work provides clear guidance for the voltage plateau manipulation of anion intercalation into two-dimensional materials.
Project description:Although aqueous zinc-ion batteries have gained great development due to their many merits, the frozen aqueous electrolyte hinders their practical application at low temperature conditions. Here, the synergistic effect of cation and anion to break the hydrogen-bonds network of original water molecules is demonstrated by multi-perspective characterization. Then, an aqueous-salt hydrates deep eutectic solvent of 3.5 M Mg(ClO4)2 + 1 M Zn(ClO4)2 is proposed and displays an ultralow freezing point of - 121 °C. A high ionic conductivity of 1.41 mS cm-1 and low viscosity of 22.9 mPa s at - 70 °C imply a fast ions transport behavior of this electrolyte. With the benefits of the low-temperature electrolyte, the fabricated Zn||Pyrene-4,5,9,10-tetraone (PTO) and Zn||Phenazine (PNZ) batteries exhibit satisfactory low-temperature performance. For example, Zn||PTO battery shows a high discharge capacity of 101.5 mAh g-1 at 0.5 C (200 mA g-1) and 71 mAh g-1 at 3 C (1.2 A g-1) when the temperature drops to - 70 °C. This work provides an unique view to design anti-freezing aqueous electrolyte.
Project description:Multivalent-ion batteries are emerging as low-cost, high energy density, and safe alternatives to Li-ion batteries but are challenged by slow cation diffusion in electrode materials due to the high polarization strength of Mg- and Al-ions. In contrast, Ca-ion has a low polarization strength similar to that of Li-ion, therefore a Ca-ion battery will share the advantages while avoiding the kinetics issues related to multivalent batteries. However, there is no battery known that utilizes the Ca-ion chemistry due to the limited success in Ca-ion storage materials. Here, a safe and low-cost aqueous Ca-ion battery based on a highly reversible polyimide anode and a high-potential open framework copper hexacyanoferrate cathode is demonstrated. The prototype cell shows a stable capacity and high efficiency at both high and low current rates, with an 88% capacity retention and an average 99% coloumbic efficiency after cycling at 10C for 1000 cycles. The Ca-ion storage mechanism for both electrodes as well as the origin of the fast kinetics have been investigated. Additional comparison with a Mg-ion cell with identical electrodes reveals clear kinetics advantages for the Ca-ion system, which is explained by the smaller ionic radii and more facile desolvation of hydrated Ca-ions.
Project description:Aqueous Zn ion batteries (ZIBs) are promising in energy storage due to the low cost, high safety, and material abundance. The development of metal oxides as the cathode for ZIBs is limited by the strong electrostatic forces between O2- and Zn2+ which leads to poor cyclic stability. Herein, Bi2S3 is proposed as a promising cathode material for rechargeable aqueous ZIBs. Improved cyclic stability and fast diffusion of Zn2+ is observed. Also, the layered structure of Bi2S3 with the weak van der Waals interaction between layers offers paths for diffusion and occupancy of Zn2+. As a result, the Zn/Bi2S3 battery delivers high capacity of 161 mAh g-1 at 0.2 A g-1 and good cycling stability up to 100 cycles with ca. 100% retention. The battery also demonstrates good cyclic performance of ca. 80.3% over 2000 cycles at 1 A g-1. The storage mechanism in the Bi2S3 cathode is related to the reversible Zn ion intercalation/extraction reactions and the capacitive contribution. This work indicates that Bi2S3 shows great potential as the cathode of ZIBs with good performance and stability.
Project description:The utilization of monomeric, lower phosphorous oxides and oxoanions, such as metaphosphite (PO2 - ), which is the heavier homologue of the common nitrite anion but previously only observed in the gas phase and by matrix isolation, requires new synthetic strategies. Herein, a series of rhenium(I-III) complexes with PO2 - as ligand is reported. Synthetic access was enabled by selective oxygenation of a terminal phosphide complex. Spectroscopic and computational examination revealed slightly stronger ?-donor and comparable ?-acceptor properties of PO2 - compared to homologous NO2 - , which is one of the archetypal ligands in coordination chemistry.
Project description:Self-charging power systems integrating energy harvesting technologies and batteries are attracting extensive attention in energy technologies. However, the conventional integrated systems are highly dependent on the availability of the energy sources and generally possess complicated configuration. Herein, we develop chemically self-charging aqueous zinc-ion batteries with a simplified two-electrode configuration based on CaV6O16·3H2O electrode. Such system possesses the capability of energy harvesting, conversion and storage simultaneously. It can be chemically self-recharged by the spontaneous redox reaction between the discharged cathode and oxygen from the ambient environment. Chemically self-recharged zinc-ion batteries display an initial open-circuit voltage of about 1.05?V and a considerable discharge capacity of about 239?mAh?g-1, indicating the excellent self-rechargeability. Impressively, such chemically self-charging zinc-ion batteries can also work well at chemical or/and galvanostatic charging hybrid modes. This work not only provides a route to design chemically self-charging energy storage, but also broadens the horizons of aqueous zinc-ion batteries.
Project description:Sodium ion batteries are being considered as an alternative to lithium ion batteries in large-scale energy storage applications owing to the low cost. A novel titanate compound, NaAlTi3O8, was successfully synthesized and tested as a promising anode material for sodium ion batteries. Powder X-ray Diffraction (XRD) and refinement were used to analyze the crystal structure. Electrochemical cycling tests under a C/10 rate between 0.01 - 2.5 V showed that ~83 mAh/g capacity could be achieved in the second cycle, with ~75% of which retained after 100 cycles, which corresponds to 0.75 Na+ insertion and extraction. The influence of synthesis conditions on electrochemical performances was investigated and discussed. NaAlTi3O8 not only presents a new anode material with low average voltage of ~0.5 V, but also provides a new type of intercalation anode with a crystal structure that differentiates from the anodes that have been reported.
Project description:Mechanochemical synthesis of Si/Cu3Si-based composite as negative electrode materials for lithium ion battery is investigated. Results indicate that CuO is decomposed and alloyed with Si forming amorphous Cu-Si solid solution due to high energy impacting during high energy mechanical milling (HEMM). Upon carbonization at 800 °C, heating energy induces Cu3Si to crystallize in nanocrystalline/amorphous Si-rich matrix enhancing composite rigidity and conductivity. In addition, residual carbon formed on outside surface of composite powder as a buff space further alleviates volume change upon lithiation/delithiation. Thus, coin cell made of C-coated Si/Cu3Si-based composite as negative electrode (active materials loading, 2.3 mg cm-2) conducted at 100 mA g-1 performs the initial charge capacity of 1812 mAh g-1 (4.08 mAh cm-2) columbic efficiency of 83.7% and retained charge capacity of 1470 mAh g-1 (3.31 mAh cm-2) at the end of the 100th cycle, opening a promised window as negative electrode materials for lithium ion batteries.
Project description:Fast lithium ion and electron transport inside electrode materials are essential to realize its superb electrochemical performances for lithium rechargeable batteries. Herein, a distinctive structure of cathode material is proposed, which can simultaneously satisfy these requirements. Nanosized Li3V2(PO4)3 (LVP) particles can be successfully grown up on the carbon nanofiber via electrospinning method followed by a controlled heat-treatment. Herein, LVP particles are anchored onto the surface of carbon nanofiber, and with this growing process, the size of LVP particles as well as the thickness of carbon nanofiber can be regulated together. The morphological features of this composite structure enable not only direct contact between electrolytes and LVP particles that can enhance lithium ion diffusivity, but also fast electron transport through 1D carbon network along nanofibers simultaneously. Finally, it is demonstrated that this unique structure is an ideal one to realize high electron transport and ion diffusivity together, which are essential for enhancing the electrochemical performances of electrode materials.
Project description:A V4+-V2O5 cathode with mixed vanadium valences was prepared via a novel synthetic method using VOOH as the precursor, and its zinc-ion storage performance was evaluated. The products are hollow spheres consisting of nanoflakes. The V4+-V2O5 cathode exhibits a prominent cycling performance, with a specific capacity of 140 mAh g-1 after 1000 cycles at 10 A g-1, and an excellent rate capability. The good electrochemical performance is attributed to the presence of V4+, which leads to higher electrochemical activity, lower polarization, faster ion diffusion, and higher electrical conductivity than V2O5 without V4+. This engineering strategy of valence state manipulation may pave the way for designing high-performance cathodes for elucidating advanced battery chemistry.