Understanding and controlling the sulfur reduction species (Li2Sx, 1 ≤ x ≤ 8) under realistic battery conditions are essential for the development of advanced practical Li-S cells that can reach their full theoretical capacity. However, it has been a great challenge to probe the sulfur reduction intermediates and products because of the lack of methods. This work employed various ex situ and in situ methods to study the mechanism of the Li-S redox reactions and the properties of Li2Sx and Li2S. Synchrotron high-energy X-ray diffraction analysis used to characterize dry powder deposits from lithium polysulfide solution suggests that the new crystallite phase may be lithium polysulfides. The formation of Li2S crystallites with a polyhedral structure was observed in cells with both the conventional (LiTFSI) electrolyte and polysulfide-based electrolyte. In addition, an in situ transmission electron microscopy experiment observed that the lithium diffusion to sulfur during discharge preferentially occurred at the sulfur surface and formed a solid Li2S crust. This may be the reason for the capacity fade in Li-S cells (as also suggested by EIS experiment in Supporting Information ). The results can be a guide for future studies and control of the sulfur species and meanwhile a baseline for approaching the theoretical capacity of the Li-S battery.
Today there is a consensus regarding the potential of NaBH4 as a good candidate for hydrogen storage and release via hydrolysis reaction, especially for mobile, portable and niche applications. However as gone through in the present paper two main issues, which are the most investigated throughout the open literature, still avoid NaBH4 to be competitive. The first one is water handling. The second one is the catalytic material used to accelerate the hydrolysis reaction. Both issues are objects of great attentions as it can be noticed throughout the open literature. This review presents and discusses the various strategies which were considered until now by many studies to manage water and to improve catalysts performances (reactivity and durability). Published studies show real improvements and much more efforts might lead to significant overhangs. Nevertheless, the results show that we are still far from envisaging short‐term commercialisation.
A new orthophosphate α-Na2Ni2Fe(PO4)3 was synthesized using a solid state reaction route, and its crystal structure was determined from powder X-ray diffraction data. The physical properties of α-Na2Ni2Fe(PO4)3 were studied by magnetic and electrochemical measurements and by Mössbauer and Raman spectroscopy. α-Na2Ni2Fe(PO4)3 crystallizes according to a stuffed α-CrPO4-type structure with the space group Imma and the cell parameters a = 10.42821(12), b = 13.19862(15), c = 6.47634(8) Å, and Z = 4. The structure consists of a 3D-framework of octahedra and tetrahedra sharing corners and/or edges with channels along [100] and [010], in which the sodium atoms are located. The (57)Fe Mössbauer spectrum indicates that the Fe(3+) cation is distributed over two crystallographic sites implying the presence of a Ni(2+)/Fe(3+) statistical disorder. Magnetic susceptibility follows the Curie-Weiss behavior above 100 K with θ = -114.3 K indicating the occurrence of predominant antiferromagnetic interactions. Electrochemical tests indicate that during the first discharge to 1 V vs. Na(+)/Na in a sodium cell, one Na(+) ion could be inserted into the α-Na2Ni2Fe(PO4)3 structure. This has led to the formation of a new phase Na3Ni2Fe(PO4)3 which was found to be promising as a positive electrode material for sodium batteries. When α-Na2Ni2Fe(PO4)3 is further discharged to 0.03 V, it delivers a capacity of 960 mA h g(-1). This corresponds to the intercalation of more than seven sodium atoms per formula unit which is an indication of a conversion-type behaviour with the formation of metallic Fe and Ni. When cycled in the voltage range 0.03-3 V vs. Na(+)/Na, at 20 °C, under the current rates of 50, 100, 200, and 400 mA g(-1), reversible capacities of 238, 196, 153, and 115 mA h g(-1), were obtained, respectively.
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