Akira Sugahara

MXene as a Charge Storage Host

The development of efficient electrochemical energy storage (EES) devices is an important sustainability issue to realize green electrical grids. Charge storage mechanisms in present EES devices, such as ion (de)intercalation in lithium-ion batteries and electric double layer formation in capacitors, provide insufficient efficiency and performance for grid use. Intercalation pseudocapacitance (or redox capacitance) has emerged as an alternative chemistry for advanced EES devices. Intercalation pseudocapacitance occurs through bulk redox reactions with ultrafast ion diffusion. In particular, the metal carbide/nitride nanosheets termed MXene discovered in 2011 are a promising class of intercalation pseudocapacitor electrode materials because of their compositional versatility for materials exploration (e.g., Ti2CT x, Ti3C2T x, V2CT x, and Nb2CT x, where T is a surface termination group such as F, Cl, O, or OH), high electrical conductivity for high current charge, and a layered structure of stacked nanosheets for ultrafast ion intercalation. Various MXene electrodes have been reported to exhibit complementary battery performance, such as large specific capacity at high charge/discharge rates. However, general design strategies of MXenes for EES applications have not been established because of the limited understanding of the electrochemical mechanisms of MXenes. This Account describes current knowledge of the fundamental electrochemical properties of MXenes and attempts to clarify where intercalation capacitance ends and intercalation pseudocapacitance begins. MXene electrodes in aqueous electrolytes exhibit intercalation of hydrated cations. The hydrated cations form an electric double layer in the interlayer space to give a conventional capacitance within the narrow potential window of aqueous electrolytes. When nonaqueous electrolytes are used, although solvated cations are intercalated into the interlayer space during the initial stage of charging, the confined solvation shell should gradually collapse because of the large inner potential difference in the interlayer space. Upon further charging, desolvated ions solely intercalate, and the atomic orbitals of the desolvated cations overlap with the orbitals of MXene to form a donor band. The formation of the donor band induces the reduction of MXene, giving rise to an intercalation pseudocapacitance through charge transfer from the ions to MXene sheets. Differences in the electrochemical reaction mechanisms lead to variation of the electrochemical responses of MXenes (e.g., cyclic voltammetry curves, specific capacitance), highlighting the importance of establishing a comprehensive grasp of the electrochemical reactions of MXenes at an atomic level. Because of their better charge storage kinetics compared with those of typical materials used in present EES devices, aqueous/nonaqueous asymmetric capacitors using titanium carbide MXene electrodes are capable of efficient operation at high charge/discharge rates. Therefore, the further development of novel MXene electrodes for advanced EES applications is warranted.

Isomerization effect of counter anion on the spin crossover transition in [Fe(4-NH2trz)3](CH3C6H4SO3)2?nH2O

We have investigated the spin crossover transition of the triazole bridged one dimensional FeII complexes, [Fe(4-NH2trz)3](o-, m-, p-tos)2nH2O (tosH = toluenesulfonic acid), in order to study the isomerization effect of counter anion on the spin crossover phenomenon by means of 57Fe Mossbauer spectroscopy and magnetic susceptibility measurement. In the heating process, the spin transition of the all salts occurs around room temperatures, i.e. those of o-, m-, p-tos salts are 330 K, 319 K and 320 & 350 K, respectively. In the cooling process, the structural isomerization effect of counter anion on the spin crossover phenomenon is more remarkable than that in the heating process. In the case of o-tos salt, the spin transition occurs at 250 K with thermal hysteresis of 80 K. On the other hand, in the case of the m-tos salt, the spin transition occurs abruptly at 319 K with negligible small hysteresis. In the case of the p-tos salt, the spin transition occurs abruptly at 295 K in the cooling process in spite of stepwise spin transitions in the heating process.