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Herein, the Cu 2 P 2 O 7 /carbon-nanotube nanocomposite is reported as a cathode material based on a conversion reaction for rechargeable sodium batteries (RSBs). The nanocomposite electrode exhibits the large capacity of 355 mAh g -1 , which is consistent with the 4 mol Na + storage per formula unit determined by first-principles calculation. Its average operation voltage is approximately 2.4 V (vs Na + /Na). Even at 1800 mA g -1 , a capacity of 223 mAh g -1 is maintained. Moreover, the composite electrode exhibits acceptable capacity retention of over 75% of the initial capacity for 300 cycles at 360 mA g -1 . The overall conversion reaction mechanism on the Cu 2 P 2 O 7 /carbon-nanotube nanocomposite is determined to be Cu 2 P 2 O 7 + 4Na + + 4e - → 2Cu + Na 4 P 2 O 7 based on operando/ex situ structural and physicochemical analyses. The high energy density of the Cu 2 P 2 O 7 /carbon-nanotube nanocomposite (720 Wh kg -1 ) supported by this conversion chemistry indicates a high possibility of application of this material as a promising cathode candidate for RSBs.

Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0, 0.05) cathode materials, which allow extraction of 3 mol of Li from the formula unit, were investigated to achieve a high energy density utilizing multielectron reactions, activated by the V 3+/5+ redox reaction. Structural investigation demonstrates that V 3+ was replaced by equivalent Mn 3+ , as confirmed by Rietveld refinement of the X-ray diffraction data and X-ray absorption near edge spectroscopy. The substitution simultaneously lowered the band gap energy from 3.4 to 3.2 eV, according to a density functional theory calculation. In addition to the effect of Mn doping, surface carbonization of Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0, 0.05) dramatically increased the electric conductivity up to 10 -3 S cm -1 . As a result, the carbon-coated Li 3 V 2-x Mn x (PO 4 ) 3 (x = 0.05) delivered a high discharge (reduction) capacity of approximately 180 mAh g -1 at a current of 20 mA g -1 (0.1 C rate) with excellent retention, delivering approximately 163 mAh g -1 at the 200th cycle. Even at 50 C (10 A g -1 ), the electrode afforded a discharge capacity of 68 mAh g -1 and delivered approximately 104 mAh g -1 (1 C) at -10 °C with the help of Mn doping and carbon coating. The synergetic effects such as a lowered band gap energy by Mn doping and high electric conductivity associated with carbon coating are responsible for the superior electrode performances, including thermal properties with extremely low exothermic heat generation (<0.4 J g -1 for Li 0.02 V 1.95 Mn 0.05 (PO 4 ) 3 ), which is compatible with the layered high energy density of LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 0.8 Co 0.1 Mn 0.1 O 2 materials.

The development of a water oxidation catalyst has been a demanding challenge for the realization of overall water-splitting systems. Although intensive studies have explored the role of Mn element in water oxidation catalysis, it has been difficult to understand whether the catalytic capability originates mainly from either the Mn arrangement or the Mn valency. In this study, to decouple these two factors and to investigate the role of Mn valency on catalysis, we selected a new pyrophosphate-based Mn compound (Li2MnP2O7), which has not been utilized for water oxidation catalysis to date, as a model system. Due to the monophasic behavior of Li2MnP2O7 with delithiation, the Mn valency of Li(2-x)MnP2O7 (x = 0.3, 0.5, 1) can be controlled with negligible change in the crystal framework (e.g., volume change ~1%). Moreover, inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, ex-situ X-ray absorption near-edge structure, galvanostatic charging-discharging, and cyclic voltammetry analysis indicate that Li(2-x)MnP2O7 (x = 0.3, 0.5, 1) exhibits high catalytic stability without additional delithiation or phase transformation. Notably, we observed that, as the averaged oxidation state of Mn in Li(2-x)MnP2O7 increases from 2 to 3, the catalytic performance is enhanced in the series Li2MnP2O7 < Li(1.7)MnP2O7 < Li(1.5)MnP2O7 < LiMnP2O7. Moreover, Li2MnP2O7 itself exhibits superior catalytic performance compared with MnO or MnO2. Our study provides valuable guidelines for developing an efficient Mn-based catalyst under neutral conditions with controlled Mn valency and atomic arrangement.

Large-scale electric energy storage is a key enabler for the use of renewable energy. Recently, the room-temperature Na-ion battery has been rehighlighted as an alternative low-cost technology for this application. However, significant challenges such as energy density and long-term stability must be addressed. Herein, we introduce a novel cathode material, Na1.5VPO4.8F0.7, for Na-ion batteries. This new material provides an energy density of ~600 Wh kg(-1), the highest value among cathodes, originating from both the multielectron redox reaction (1.2 e(-) per formula unit) and the high potential (~3.8 V vs Na(+)/Na) of the tailored vanadium redox couple (V(3.8+)/V(5+)). Furthermore, an outstanding cycle life (~95% capacity retention for 100 cycles and ~84% for extended 500 cycles) could be achieved, which we attribute to the small volume change (2.9%) upon cycling, the smallest volume change among known Na intercalation cathodes. The open crystal framework with two-dimensional Na diffusional pathways leads to low activation barriers for Na diffusion, enabling excellent rate capability. We believe that this new material can bring the low-cost room-temperature Na-ion battery a step closer to a sustainable large-scale energy storage system.

The three-dimensional network of TiO(2) hollow nanoribbons designed from a peptide assembly using atomic layer deposition is demonstrated as a promising Li secondary battery electrode in this study. The nanoribbon network ensures effective transport of electrons and Li ions due to (i) a well-connected network of nanoribbons and (ii) the hollow structure of each nanoribbon itself, into which Li ions in the electrolyte can readily diffuse. The improved specific capacity, rate capability, and cyclability of the nanonetwork show that the utilization of a nanonetwork of individual hollow ribbons can serve as a promising strategy toward the development of high-performance electrode for Li secondary batteries.