The main drawbacks of today's state‐of‐the‐art lithium–air (Li–air) batteries are their low energy efficiency and limited cycle life due to the lack of earth‐abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo3P) nanoparticles with an exceptional activity—ORR and OER current densities of 7.21 and 6.85 mA cm−2at 2.0 and 4.2 V versus Li/Li+, respectively—in an oxygen‐saturated non‐aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance—Tafel slopes of 35 and 38 mV dec−1for ORR and OER, respectively—resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li–air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo3P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials.
Solar rechargeable battery combines the advantages of photoelectrochemical devices and batteries and has emerged as an attractive alternative to artificial photosynthesis for large‐scale solar energy harvesting and storage. Due to the low photovoltages by the photoelectrodes, however, most previous demonstrations of unassisted photocharge have been realized on systems with low open circuit potentials (<0.8 V). In response to this critical challenge, here it is shown that the combined photovoltages exceeding 1.4 V can be obtained using a Ta3N5nanotube photoanode and a GaN nanowire/Si photocathode with high photocurrents (>5 mA cm–2). The photoelectrode system makes it possible to operate a 1.2 V alkaline anthraquinone/ferrocyanide redox battery with a high ideal solar‐to‐chemical conversion efficiency of 3.0% without externally applied potentials. Importantly, the photocharged battery is successfully discharged with a high voltage output.
more » « less- NSF-PAR ID:
- 10035989
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 29
- Issue:
- 26
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Abstract Vanadium multiredox‐based NASICON‐Na
z V2−y My (PO4)3(3 ≤z ≤ 4; M = Al3+, Cr3+, and Mn2+) cathodes are particularly attractive for Na‐ion battery applications due to their high Na insertion voltage (>3.5 V vs Na+/Na0), reversible storage capacity (≈150 mA h g−1), and rate performance. However, their practical application is hindered by rapid capacity fade due to bulk structural rearrangements at high potentials involving complex redox and local structural changes. To decouple these factors, a series of Mg2+‐substituted Na3+y V2−y Mgy (PO4)3(0 ≤y ≤ 1) cathodes is studied for which the only redox‐active species is vanadium. While X‐ray diffraction (XRD) confirms the formation of solid solutions between they = 0 and 1 end members, X‐ray absorption spectroscopy and solid‐state nuclear magnetic resonance reveal a complex evolution of the local structure upon progressive Mg2+substitution for V3+. Concurrently, the intercalation voltage rises from 3.35 to 3.45 V, due to increasingly more ionic VO bonds, and the sodium (de)intercalation mechanism transitions from a two‐phase fory ≤ 0.5 to a solid solution process fory ≥ 0.5, as confirmed by in operando XRD, while Na‐ion diffusion kinetics follow a nonlinear trend across the compositional series. -
Abstract Exceeding the energy density of lithium−carbon monofluoride (Li−CFx), today's leading Li primary battery, requires an increase in fluorine content (
x ) that determines the theoretical capacity available from C−F bond reduction. However, high F‐content carbon materials face challenges such as poor electronic conductivity, low reduction potentials (<1.3 V versus Li/Li+), and/or low C−F bond utilization. This study investigates molecular structural design principles for a new class of high F‐content fluoroalkyl‐aromatic catholytes that address these challenges. A polarizable conjugated system—an aromatic ring with an alkene linker—functions as electron acceptor and redox initiator, enabling a cascade defluorination of an adjacent perfluoroalkyl chain (R F= −CnF2n+1). The synthesized molecules successfully overcome premature deactivation observed in previously studied catholytes and achieve close‐to‐full defluorination (up to 15/17 available F), yielding high gravimetric capacities of 748 mAh g−1fluoroalkyl‐aromaticand energies of 1785 Wh kg−1fluoroalkyl‐aromatic. The voltage compatibility between fluoroalkyl‐aromatics and CFxenables design of hybrid cells containing C−F redox activity in both solid and liquid phases, with a projected enhancement of Li–CFxgravimetric energy by 35% based on weight of electrodes+electrolyte. With further improvement of cathode architecture, these “liquid CFx” analogues are strong candidates for exceeding the energy limitations of today's primary chemistries. -
Abstract 1D materials, such as nanofibers or nanoribbons are considered as the future ultimate limit of downscaling for modern electrical and electrochemical devices. Here, for the first time, nanofibers of a solid solution transition metal trichalcogenide (TMTC), Nb1‐
x Tax S3, are successfully synthesized with outstanding electrical, thermal, and electrochemical characteristics rivaling the performance of the‐state‐of‐the art materials for each application. This material shows nearly unchanged sheet resistance (≈740 Ω sq−1) versus bending cycles tested up to 90 cycles, stable sheet resistance in ambient conditions tested up to 60 days, remarkably high electrical breakdown current density of ≈30 MA cm−2, strong evidence of successive charge density wave transitions, and outstanding thermal stability up to ≈800 K. Additionally, this material demonstrates excellent activity and selectivity for CO2conversion to CO reaching ≈350 mA cm−2at −0.8 V versus RHE with a turnover frequency number of 25. It also exhibits an excellent performance in a high‐rate Li–air battery with the specific capacity of 3000 mAh g−1at a current density of 0.3 mA cm−2. This study uncovers the multifunctionality in 1D TMTC alloys for a wide range of applications and opens a new direction for the design of the next generation low‐dimensional materials. -
Abstract Li2MnO3has been contemplated as a high‐capacity cathode candidate for Li‐ion batteries; however, it evolves oxygen during battery charging under ambient conditions, which hinders a reversible reaction. However, it is unclear if this irreversible process still holds under subambient conditions. Here, the low‐temperature electrochemical properties of Li2MnO3in an aqueous LiCl electrolyte are evaluated and a reversible discharge capacity of 302 mAh g−1at a potential of 1.0 V versus Ag/AgCl at −78 °C with good rate capability and stable cycling performance, in sharp contrast to the findings in a typical Li2MnO3cell cycled at room temperature, is observed. However, the results reveal that the capacity does not originate from the reversible oxygen oxidation in Li2MnO3but the reversible Cl2(l)/Cl−(aq.) redox from the electrolyte. The results demonstrate the good catalytic properties of Li2MnO3to promote the Cl2/Cl−redox at low temperatures.