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ZrCo alloy has been considered as a tritium storage material to replace uranium for large-scale hydrogen isotope storage and delivery in tritium plant of the magnetic confinement nuclear fusion reactor. However, the disproportionation of ZrCo greatly obstructed its aspects to engineering application. A multifaceted understanding about the intrinsic nature of disproportionation reaction, and proposing anti-disproportionation strategies from material design have always been the bottleneck and hotspot in the tritium science and technology field. Herein, we studied the anti-disproportionation properties of Zr(Ti)Co alloy with thin film structure, and the effects of film thickness and Ti substitutions on the anti-disproportionation properties of the films were obtained. Firstly, a series of ZrCo films with different deposited time were prepared by magnetron sputtering instrument. The disproportionation ratio of the 2 h deposited ZrCo film (1.641μm) is 23.9%, and attenuated with the increase of film thickness. It indicates that the anti-disproportionation properties of the film structure is significantly better than that of ZrCo particle (68%). The microtopography analysis shows that the micro stress in the film structure is beneficial to hinder the disproportionation process. However, the hydrogenation reaction is also obviously inhibited in the ZrCo film. In addition, Ti doping can further improve its anti-disproportionation performance (10.3–7.3% for the 2 h deposited Zr 1-x Ti x Co film) without significantly reducing the hydrogen absorption capacities of the ZrCo flims. The anti-disproportionation performance is closely related to the weakened interaction between Zr and H atoms, after Ti doping into the ZrCo flim, leading to the impaired driving force for disproportionation reaction. The study in this work can provide an important reference for the anti-disproportionation modification of ZrCo alloys. • Hydrogen storage performance of ZrCo with film structure were investigated. • Anti-disproportionation behavior of ZrCo film is related to thickness. • Anti-disproportionation properties of ZrCo film is better than that of particles. • The Ti doping improve the anti-disproportionation performance of ZrCo films. • The Ti enhancement mechanism was obtained from the perspective of binding energy. [ABSTRACT FROM AUTHOR]

Cycling stability of ZrCo–H system is extremely important for the long-term operation of the storage and delivery system (SDS) in ITER. Herein, the optimal cycling operation parameters were systematically investigated. It indicates that various parameters, such as hydrogen pressure, temperature, composition, and stoichiometric ratio of H atoms, will all affect the cycling performance of the ZrCo–H system significantly. The decline rate of the hydrogen capacity of the ZrCo–H system is positively correlated with the hydrogen pressure. The experimental result shows that 54% of hydrogen capacity decreases under 28.1 kPa hydrogen pressure, while 30% of attenuation is obtained when the pressure is decreased to 8.1 kPa after 14 cycles. In terms of temperature, the lowest cycling attenuation can be maintained at about 25% after 14 cycles when the dehydrogenation temperature at 550 °C. The effects of doping elements, Hf and Ti, on the cycling stability of ZrCo–H system are also compared. The Zr 0.8 Ti 0.2 Co sample exhibits higher cycling capacity than ZrCo and Zr 0.8 Hf 0.2 Co samples. The extremely excellent behavior can be achieved when all ZrCo alloys are continuously evacuated during the hydrogen release process, and the attenuation of only 1.1% is observed for Zr 0.8 Ti 0.2 Co after 15 cycles. Besides, the cycling attenuation is related to residual stoichiometric ratio of H atoms in ZrCo alloy during the cycling test. When the residual H atoms proportion exceeds 1 in ZrCo during dehydrogenation, hydrogen cycling capacity hardly fades. The XRD results reveal that the disproportionation of ZrCo is directly associated with the cycling degradation, yielding the more stable products of ZrCo 2 and ZrH 2 , However, the disproportionation can be avoided during the cycling process by controlling the stoichiometric ratio of H atoms remained in ZrCo above 1. This study demonstrates that the cycling performance of ZrCo can be substantially improved when the operation parameters are properly adjusted, which provides a significant important reference for durable running of SDS in ITER. • Relationship between cyclic property and operation parameters of ZrCo is revealed. • Residual H ratio above 1 in ZrCo after desorption indeed improves cyclic stability. • Cycling capacity retention ratio maintains at ~99% for the optimized parameter. [ABSTRACT FROM AUTHOR]