Lithium metal batteries (LMBs) hold the promise to pushing cell level energy densities beyond 300 Wh kg −1 while operating at ultra-low temperatures (< −30°C). Batteries capable of both charging and discharging at these temperature extremes are highly desirable due to their inherent reduction of external warming requirements. Here we demonstrate that the local solvation structure of the electrolyte defines the charge-transfer behavior at ultra-low temperature, which is crucial for achieving high Li metal coulombic efficiency (CE) and avoiding dendritic growth. These insights were applied to Li metal full cells, where a high-loading 3.5 mAh cm −2 sulfurized polyacrylonitrile (SPAN) cathode was paired with a one-fold excess Li metal anode. The cell retained 84 % and 76 % of its room temperature capacity when cycled at −40 and −60 °C, respectively, which presented stable performance over 50 cycles. This work provides design criteria for ultra-low temperature LMB electrolytes, and represents a defining step for the performance of low-temperature batteries.
Rechargeable lithium-ion batteries with high energy density that can be safely charged and discharged at high rates are desirable for electrified transportation and other applications 1-3. However, the sub-optimal intercalation potentials of current anodes result in a trade-off between energy density, power and safety. Here we report that disordered rock salt 4,5 Li3+xV2O5 can be used as a fast-charging anode that can reversibly cycle two lithium ions at an average voltage of about 0.6 volts versus a Li/Li + reference electrode. The increased potential compared to graphite 6,7 reduces the likelihood of lithium metal plating if proper charging controls are used, alleviating a major safety concern (short-circuiting related to Li dendrite growth). In addition, a lithium-ion battery with a disordered rock salt Li3V2O5 anode yields a cell voltage much higher than does a battery using a commercial fastcharging lithium titanate anode or other intercalation anode candidates (Li3VO4 and LiV0.5Ti0.5S2) 8,9. Further, disordered rock salt Li3V2O5 can perform over 1,000 charge-discharge cycles with negligible capacity decay and exhibits exceptional rate capability, delivering over 40 per cent of its capacity in 20 seconds. We attribute the low voltage and high rate capability of disordered rock salt Li3V2O5 to a redistributive lithium intercalation mechanism with low energy barriers revealed via ab initio calculations. This low-potential, high-rate intercalation reaction can be used to identify other metal oxide anodes for fast-charging, long-life lithium-ion batteries.
A combined ab initio and experimental investigation has been performed of the main features of the electronic spectrum of acetone. Vertical transition energies have been calculated from the ground to the n y →*, →*, →*, and the nϭ3 Rydberg states. In addition, the 1 A 1 energy surfaces have been studied as functions of the CO bond length. The 1 A 1 3 p and 3d states were found to be heavily perturbed by the →* state. Resonant multiphoton ionization and polarization-selected photoacoustic spectra of acetone have been measured and observed transitions were assigned on internal criteria. The calculated vertical transition energies to the n y →* and all Rydberg states were found to be in agreement with experiment. This includes the 3s-, all three 3 p-, and the A 1 , B 1 , and B 2 3d-Rydberg states. By contrast, there is little agreement between the calculated and experimental relative intensities of the A 1 and B 2 3d-Rydberg transitions. In addition, anomalously intense high vibrational overtone bands of one of the 3 p-Rydberg transitions have been observed. These results confirm the strong perturbation of the 3 p-and 3d-Rydberg states by the →* state found in the theoretical calculation and support the calculated position of this unobserved state.
Aqueous batteries with zinc metal anodes are promising alternatives to Li-ion batteries for grid storage because of their abundance and benefits in cost, safety, and nontoxicity. However, short cyclability due to zinc dendrite growth remains a major obstacle. Here, we report a cross-linked polyacrylonitrile (PAN)-based cation exchange membrane that is low cost and mechanically robust. Li 2 S 3 reacts with PAN, simultaneously leading to cross-linking and formation of sulfur-containing functional groups. Hydrolysis of the membrane results in the formation of a membrane that achieves preferred cation transport and homogeneous ionic flux distribution. The separator is thin (30 μm-thick), almost 9 times stronger than hydrated Nafion, and made of low-cost materials. The membrane separator enables exceptionally long cyclability (>350 cycles) of Zn/Zn symmetric cells with low polarization and effective dendrite suppression. Our work demonstrates that the design of new separators is a fruitful pathway to enhancing the cyclability of aqueous batteries.
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