A review of classical hydrogen isotopes storage materials

Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.

Diluent decomposition-assisted formation of Li F-rich solid-electrolyte interfaces enables high-energy Li-metal batteries

Passivation by the inorganic-rich solid electrolyte interphase(SEI),especially the LiF-rich SEI,is highly desirable to guarantee the durable lifespan of Li metal batteries(LMBs).Here,we report a diluent with the capability to facilitate the formation of LiF-rich SEI while avoiding the excess consumption of Li salts.Dissimilar to most of reported inert diluents,heptafluoro-l-methoxypropane(HM) is firstly demonstrated to cooperate with the decomposition of anions to generate LiF-rich SEI via releasing Fcontaining species near Li surface.The designed electrolyte consisting of 1.8 M LiFSI in the mixture of1,2-dimethoxyethane(DME)/HM(2:1 by vol.) achieves excellent compatibility with both Li metal anodes(Coulombic efficiency~99.8%) and high-voltage cathodes(4.4 V LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811) and 4.5 V LiCoO_(2)(LCO) vs Li^(+)/Li).The 4.4 V Li(20μm)‖NMC811(2.5 mA h cm^(-2)) and 4.5 V Li(20μm)‖LCO(2.5 mA h cm^(-2)) cells achieve capacity retentions of 80% over 560 cycles and 80% over 505 cycles,respectively.Meanwhile,the anode-free pouch cell delivers an energy density of~293 W h kg^(-1)initially and retains 70% of capacity after 100 deep cycles.This work highlights the critical impact of diluent on the SEI formation,and opens up a new direction for designing desirable interfacial chemistries to enable high-performance LMBs.

Superior de/hydrogenation performances of MgH2 catalyzed by 3D flower-like TiO2@C nanostructures

Magnesium hydride has been seen as a potential material for solid state hydrogen storage,but the kinetics and thermodynamics obstacles have hindered its development and application.Three-dimensional flower-like TiO2@C and TiO2 were synthesized as the catalyst for MgH2 system and great catalytic activities are acquired in the hydrogen sorption properties.Experiments also show that the flower-like TiO2@C is superior to flower-like TiO2 in improving the hydrogen storage properties of MgH2.The hydrogen desorption onset and peak temperatures of flower-like TiO2 doped MgH2 is reduced to 199.2℃and 245.4℃,while the primitive MgH2 starts to release hydrogen at 294.6℃and the rapid dehydrogenation temperature is even as high as 362.6℃.The onset and peak temperatures of flower-like TiO2@C doped MgH2 are further reduced to 180.3℃and 233.0℃.The flower-like TiO2@C doped MgH2 composite can release6.0 wt%hydrogen at 250℃within 7 min,and 4.86 wt%hydrogen at 225℃within 60 min,while flowerlike TiO2 doped MgH2 can release 6.0 wt%hydrogen at 250℃within 8 min,and 3.89 wt%hydrogen at225℃within 60 min.Hydrogen absorption kinetics is also improved dramatically.Moreover,compared with primitive MgH2 and the flower-like TiO2 doped MgH2,the activation energy of flower-like TiO2@C doped MgH2 is significantly decreased to 67.10 kJ/mol.All the improvement of hydrogen sorption properties can be ascribed to the flower-like structure and the two-phase coexistence of TiO2 and amorphous carbon.Such phase composition and unique structure are proved to be the critical factor to improve the hydrogen sorption properties of MgH2,which can be considered as the new prospect for improving the kinetics of light-metal hydrogen storage materials.

Regulating local chemistry in ZrCo-based orthorhombic hydrides via increasing atomic interference for ultra-stable hydrogen isotopes storage

Developing a universal and reliable strategy for the modulation of composition and structure of energy storage materials with stable cycling performance is vital for hydrogen and its isotopes storage advanced system,yet still challenging.Herein,an ultra-stable lattice structure is designed and verified to increase atomic chaos and interference for effectively inhibiting disproportionation reaction and improving cycling stability in ZrCo-based hydrogen isotopes storage alloy.After screening in terms of configuration entropy calculation,we construct Zr_(1-2)Nb_(x)Co_(1-2x)Cu_(x)Ni_(x)(x=0.15,0.2,0.25) alloys with increased atomic chaos,and successfully achieve stable isostructural de-/hydrogenation during 100 cycles,whose cycling capacity retentions are above 99%,much higher than 22.4%of pristine ZrCo alloy.Both theoretical analysis and experimental evidences indicate the high thermo-stability of orthorhombic lattice in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy.Notably,the increased atomic chaos and interference in Zr_(0.8)Nb_(0.2)Co_(0.6)Cu_(0.2)Ni_(0.2) alloy causes regulation in hydrogen local chemical neighborhood,thereby confusing the hydrogen release order,which effectively eliminates lattice distortion and unlocks an ultrastable lattice structure.This study provides a new and comprehensive inspiration for hydrogen atoms transport behaviors and intrinsic reason of stable orthorhombic transformation,which can contribute to paving the way for other energy storage materials modulation.

Extreme high reversible capacity with over 8.0 wt% and excellent hydrogen storage properties of MgH2 combined with LiBH4 and Li3AlH6

Magnesium hydride has attracted great attention because of its high theoretical capacity and outstanding reversibility, nevertheless, its practical applications have been restricted by the disadvantages of the sluggish kinetics and high thermodynamic stability. In this work, an unexpected high reversible hydrogen capacity over 8.0 wt% has been achieved from MgH2 metal hydride composited with small amounts of LiBH4 and Li3AlH6 complex hydrides, which begins to release hydrogen at 276 ℃ and then completely dehydrogenates at 360 ℃. The dehydrogenated MgH2+LiBH4/Li3AlH6 composite can fully reabsorb hydrogen below 300 ℃ with an excellent cycling stability. The composite exhibits a significant reduction of dehydrogenation activation energy from 279.7 kJ/mol(primitive MgH2) to 139.3 kJ/mol(MgH2+LiBH4/Li3AlH6),as well as a remarkable reduction of dehydrogenation enthalpy change from 75.1 k J/mol H2(primitive MgH2) to 62.8 kJ/mol H2(MgH2+LiBH4/Li3AlH6). The additives of LiBH4 and Li3AlH6 not only enhance the cycling hydrogen capacity, but also simultaneously improve the reversible de/rehydrogenation kinetics, as well as the dehydrogenation thermodynamics. This notable improvement on the hydrogen absorption/desorption behaviors of the MgH2+LiBH4/Li3AlH6 composite could be attributed to the dehydrogenated products including Li3Mg7, Mg17Al12 and MgAlB4, which play a key role on reducing the dehydrogenation activation energy and increasing diffusion rate of hydrogen. Meanwhile, the LiBH4 and Li3AlH6 effectively destabilize MgH2 with a remarkable reduction on dehydrogenation enthalpy change in terms of thermodynamics. In particular, the Li3Mg7, Mg17Al12 and MgAlB4 phases can reversibly transform into MgH2, Li3AlH6 and LiBH4 after rehydrogenation, which contribute to maintain a high cycling capacity.This constructing strategy can further promote the development of high reversible capacity Mg-based materials with suitable de/rehydrogenation properties.

Robust architecture of 2D nano Mg-based borohydride on graphene with superior reversible hydrogen storage performance

Efficient technical strategies to synthesize hydrides with high capacity and favorable reversibility are significant for the development of novel energy materials.Herein,nano Mg-based borohydride,Mg(BH_(4))_(2),with robust architecture was designed and prepared by confining on graphene through a solution selfconfinement method.The Mg(BH_(4))_(2) confined on graphene displays a wrinkled 2D nano layer morphology within 8.8 nm thickness.Such 2D nano Mg(BH_(4))_(2) can start dehydrogenation at 67.9℃ with a high capacity of 12.0 wt.%,which is 190.5℃ lower than pristine Mg(BH_(4))_(2).The isothermal dehydrogenation tests and kinetics fitting results indicate the 2D nano Mg(BH_(4))_(2) possesses much-enhanced dehydrogenation kinetics of 31.3 kJ/mol activation energy,which is only half of pristine Mg(BH_(4))_(2).The thermodynamics of the 2D nano Mg(BH_(4))_(2) is also verified by PCT tests,of which Gibbs free energy value for the confined 2D nano Mg(BH_(4))_(2) is estimated to be-18.01 kJ/mol H_(2),lower than-16.36 kJ/mol H_(2) of pristine Mg(BH_(4))_(2).Importantly,the reversibility of the confined 2D nano Mg(BH_(4))_(2) is significantly enhanced to over 90%capacity retention with relatively kinetics stability during 10 cycles.The mechanism analyses manifest that Mg(BH_(4))_(2) exhibits stable 2D nano morphology during 10 cyclic tests,resulting in the greatly reduced H diffusion path and the improved de/rehydrogenation kinetics of the 2D nano Mg(BH_(4))_(2).Based on theoretical calculations of Mg(BH_(4))_(2) and the intermediate MgB12H12 confined on graphene,the charge transfer status of both samples is modified to facilitate de/rehydrogenation,thus leading to the significant thermodynamic improvements of the reversible hydrogen storage performances for 2D nano Mg(BH_(4))_(2).Such investigation of the Mg-based borohydride will illuminate prospective technical research of energy storage materials.

Carbon composite support improving catalytic effect of NbC nanoparticles on the low-temperature hydrogen storage performance of MgH_(2)

Ultrafine carbon-based transition metal compounds have been widely investigated as efficient catalysts for enhancing the hydrogen storage performance of magnesium hydride.In this work,the carbon ther-mal shock method is applied to synthesize the ultrafine carbon-encapsulated NbC nanoparticles with an average grain size of 17.3 nm.The MgH_(2)-10 wt%NbC/C composites show excellent low-temperature hy-drogen storage performance with the onset dehydrogenation temperature of 196.1℃,which is 92.2℃ and 98℃ lower than that of MgH_(2)-10 wt%NbC and undoped MgH_(2),respectively.Specifically,MgH_(2)-10 wt%NbC/C can absorb 6.71 wt%H_(2) at 100℃ within 30 min around and retain almost 100%reversible hydrogen desorption capacity after 10 cycles.For the catalytic mechanism,the electron transfer process between multi-valence Nb cations of in-situ formed NbH x and Mg,H atoms can greatly improve the cyclic de/rehydrogenation kinetics of MgH_(2)-NbC/C.Besides,the enhancement of dehydrogenation kinetics can also be ascribed to MgH_(2) particle refinement by NbC nanoparticles,and destabilization of the Mg-H bond caused by carbon substrate.This investigation not only proves that carbon-encapsulated NbC nanoparti-cles can greatly enhance the hydrogen storage performance of MgH_(2) but provides an idea of preparing carbon-based transition metal carbides as effective catalysts for magnesium-based hydrogen storage ma-terials.