A Quinone Anode for Lithium-Ion Batteries in Mild Aqueous Electrolytes.

Aqueous batteries could be potentially used for grid-scale energy storage owing to the use of nonflammable electrolytes and long cycle life. Recently, quinones have shown examples as redox-active materials in aqueous batteries under either strong acidic or basic conditions. However, a quinone-based battery with a less corrosive electrolyte is still rare. Given that quinone-based batteries are heavily influenced by the pH of electrolytes, we studied the influence of acid dissociation constants (pKa) of hydroquinones on their performance as solid electrode materials. We measured the pKa of anthracene-9,10-diol (AQH2 ) and benzo[1,2-b:4,5-b']dithiophene-4,8-diol (BDTDH2 ) from the Pourbaix diagrams of two para-quinone monomers [i.e., anthracene-9,10-dione (AQ) and benzo[1,2-b:4,5-b']dithiophene-4,8-dione (BDTD)]. Subsequently, their polymeric forms [i.e., poly(anthraquinonyl sulfide) (PAQS) and poly(benzo[1,2-b:4,5-b']dithiophene-4,8-dione-2,6-diyl sulfide) (PBDTDS)] were investigated as electrodes in aqueous lithium-ion cells. At pH 13, PAQS demonstrates a low capacity and poor cycle life, whereas PBDTDS shows a capacity of 196 mAh g-1 and fade rates of 0.0038 % per cycle over 4200 cycles, 0.77 % per day over 21 days. The differences in capacity and cycle stability can be explained by the difference of corresponding pKa values. A full cell with the configuration of (-)PBDTDS|2.5 m Li2 SO4 (pH 13)|LiCoO2 (+) shows a voltage of 1.08 V, a capacity of 72 mAh g-1 and ≈99.9 % of Coulombic efficiency for 500 stable cycles.

An Aqueous Ca-Ion Battery.

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.

Universal quinone electrodes for long cycle life aqueous rechargeable batteries.

Aqueous rechargeable batteries provide the safety, robustness, affordability, and environmental friendliness necessary for grid storage and electric vehicle operations, but their adoption is plagued by poor cycle life due to the structural and chemical instability of the anode materials. Here we report quinones as stable anode materials by exploiting their structurally stable ion-coordination charge storage mechanism and chemical inertness towards aqueous electrolytes. Upon rational selection/design of quinone structures, we demonstrate three systems that coupled with industrially established cathodes and electrolytes exhibit long cycle life (up to 3,000 cycles/3,500 h), fast kinetics (≥20C), high anode specific capacity (up to 200-395 mAh g-1), and several examples of state-of-the-art specific energy/energy density (up to 76-92 Wh kg-1/ 161-208 Wh l-1) for several operational pH values (-1 to 15), charge carrier species (H+, Li+, Na+, K+, Mg2+), temperature (-35 to 25 °C), and atmosphere (with/without O2), making them a universal anode approach for any aqueous battery technology.

Li3VO4 anchored graphene nanosheets for long-life and high-rate lithium-ion batteries.

Li3VO4 nanoparticles embedded in graphene nanosheets (Li3VO4@GNS) were obtained using a sol-gel method. The composite presents excellent high-rate performance with a stable capacity of 133 mA h g(-1) at 50 C and long-life performance with a capacity retention rate of 63.1% after 5000 cycles at 5 C.