Achieving a novel solvent-free regeneration of LiBH_(4) combining hydrogen storage and production in a closed material cycle

LiBH_(4) has been considered as one of the most promising energy storage materials with its ultrahigh hydrogen capacity,which can supply hydrogen through hydrolysis process or realize hydrogen-to-electricity conversion via anodic oxidation reaction of direct borohydride fuel cells(DBFCs).However,the realization of practical hydrogen applications heavily depends on the effective synthesis of high-purity LiBH_(4) and recycling of the spent fuels(LiBO_(2)·xH_(2)O).The present work demonstrates a convenient and high-efficiency solvent-free strategy for regenerating LiBH_(4) with a maximum yield close to 80%,by retrieving its by-products with MgH_(2) as a reducing agent under ambient conditions.Besides,the hydrogen released from the regeneration course can completely compensate the demand for consumed MgH_(2).The isotopic tracer method reveals that the hydrogen stored in LiBH_(4) comes from both MgH_(2) and coordinated water bound to LiBO_(2).Here,the expensive MgH_(2) can be substituted with the readily available and cost-effective MgH_(2)-Mg mixtures to simplify the regeneration route.Notably,LiBH_(4) catalyzed by CoCl_(2) can stably supply hydrogen to proton exchange membrane fuel cell(PEMFC),thus powering a portable prototype vehicle.By combining hydrogen storage,production and utilization in a closed cycle,this work offers new insights into deploying boron-based hydrides for energy applications.

Enhanced dehydrogenation kinetic properties and hydrogen storage reversibility of LiBH_4 confined in activated charcoal

LiBH4 was confined into activated charcoal（AC） by melt infiltration method（MI）, and its effects on the hydrogen sorption properties were investigated. The N2 adsorption results reveal that melt infiltration method can effectively incorporated LiBH4 into AC. It can maintain the structural integrity of the scaffold and ensure the confinement effect. The nano-confined LiBH4/AC starts to release hydrogen at around 190 °C, which is 160 °C lower than that of pure LiBH4, and reaches a hydrogen desorption capacity of 13.6% at 400 °C. When rehydrogenated under the condition of 6 MPa H2 and 350 °C, it has a reversible hydrogen storage capacity of 6%, while pure LiBH4 shows almost no reversible hydrogen storage capacity under the same condition. Mass spectrometry analysis（MS） results suggest that no diborane or other impurity gases are released in the decomposition process. The apparent activation energy of dehydrogenation of LiBH4 after confinement into AC decreases from 156.0 to 121.1 k J/mol, which leads to the eminent enhancement of dehydrogenation kinetics of LiBH4.

Layered niobium carbide enabling excellent kinetics and cycling stability of Li-Mg-B-H hydrogen storage material Layered niobium carbide enabling excellent kinetics

The Li-Mg-B-H composite(2LiBH_(4)+MgH_(2))has a high capacity of 11.4 wt%as a hydrogen storage material.However,the slow kinetics and poor cycling stability severely restrict its practical applications.In this work,a layered Nb_(2)C MXene was first synthesized and then introduced to tailor the kinetics and cycling stability of the Li-Mg-B-H composite.The milled 2LiH+MgB_(2)composites were initially hydrogenated to obtain the 2LiBH_(4)+MgH_(2)composites.The 2LiBH_(4)+MgH_(2)+5wt%Nb_(2)C can release 9.0 wt%H_(2)in 30 min at 400℃,while it is only 2.7 wt%for the undoped 2LiBH_(4)+MgH_(2).The dehydrogenation activation energies of MgH_(2)and LiBH_(4)are 123 and 154 kJ·mol^(-1)respectively for the 5 wt%Nb_(2)C-doped composite,lower than the undoped composite(164 and 165 kJ·mol^(-1)).The 2LiBH_(4)+MgH_(2)+5 wt%Nb_(2)C possesses excellent cycling stability,with the reversible capacity only slightly reduced from 9.4 wt%for the 1st cycle to 9.3 wt%for the 20th cycle.Nb_(2)C keeps stable in the composite and acts as an efficient catalyst for the Li-Mg-B-H composite.It is believed that both the layered structure and the active Nb element contribu te to the enhanced hydrogen storage performances of the Li-Mg-B-H composite.This work confirms that the Nb_(2)C MXene with layered stru cture has a significant enhancing impact on the Li-Mg-B-H hydrogen storage materials,which is different from the bulk NbC.

Enhanced hydrogen storage properties of MgH_(2) with the co-addition of LiBH_(4) and YNi_(5) alloy

MgH_(2),as one of the typical solid-state hydrogen storage materials,has attracted extensive attention.However,the slow kinetics and poor cycle stability limit its application.In this work,LiBH_(4) and YNi_(5) alloy were co-added as additives to MgH_(2) via ball milling,thereby realizing an excellent dehydrogenation per-formance and good cycle stability at 300 ℃.The MgH_(2)-0.04LiBH_(4)-0.01YNi_(5) composite can release 7 wt.%of hydrogen in around 10 min at 300 ℃ and still have a reversible hydrogen storage capacity of 6.42 wt.%after 110 cycles,with a capacity retention rate as high as 90.3%based on the second dehydrogenation capacity.The FTIR results show that LiBH_(4) can reversibly absorb and desorb hydrogen throughout the hydrogen ab/desorption process,which contributes a portion of the reversible hydrogen storage capacity to the MgH_(2)-0.04LiBH_(4)-0.01YNi_(5) composite.Due to the small amount of LiBH_(4) and YNi_(5),the dehydro-genation activation energy of MgH_(2) did not decrease significantly,nor did the dehydrogenation enthalpy(△H)change.However,the MgNi3B2 and in-situ formed YH3 during the hydrogen absorption/desorption cycles is not only beneficial to the improvement of the kinetics performance for MgH_(2) but also improves its cycle stability.This work provides a straightforward method for developing high reversible hydrogen capacity on Mg-based hydrogen storage materials with moderate kinetic performance.

Evolution and function of residual solvent in polymer-Li_2B_(12)H_(12) composite solid electrolyte

Composite solid electrolytes(CSEs) containing polymer matrices and inorganic fillers hold promise for the next generation of solid-state batteries.However,the role of residual solvents in CSEs remains controversial.This study investigated the evolution and function of the residual solvent in a polymer-Li_2B_(12)H_(12) CSE.A partial reaction occurred between Li_2B_(12)H_(12) and solvent N,N-dimethylformamide(DMF),which produced dimethylaminomethanol(DMAM) in the CSE.Density functional theory calculations have revealed that DMA M forms stronger hydrogen bonds with polyvinylidene fluoride chains than DMF,which can have a plasticizing effect on the polymer matrix,leading to lower crystallinity and quicker segment motion.Therefore,this CSE exhibited improved Li-ion conducting properties,enabling the stable cycling of Li‖LiFePO_(4) solid-state batteries.This study provided insights into the role of residual solvents in CSEs.

Ion diffusion,and hysteresis of magnesium hydride conversion electrode materials

MgH_(2),owing to a high theoretical capacity of 2038 mAh g^(−1),is regarded as a promising anode material for lithium-ion batteries(LIBs).However,the application of MgH_(2) is still far from satisfactory due to its poor cycling stability.Herein,nano-crystallization of MgH_(2) as an anode is applied for all-solid-state lithium-ion batteries(ASSLIBs)using LiBH4 as a solid-state electrolyte.The self-assembly designed MgH_(2) electrode on graphene could effectively alleviate the volume expansion,prevent the agglomeration of active substances,improve the electron transfer,and enhance the electrochemical performance of the anode material.As a result,a reversible capacity of 1214 mAh g^(−1) after 50 cycles is obtained.Significantly enhanced cycle life with a notable capacity of 597 mAh g^(−1) at a current density of 400 mA g^(−1) is delivered after 200 cycles.Further investigation on full cells also exhibits great application potential on ASSLIBs.

Hydrogen storage properties of Nb-compounds-catalyzed LiBH4-MgH2

In order to improve the hydrogen storage properties of LiBH4-MgH2 composite, two different kinds of Nb-based catalysts, NbC and NbF5, were added to LiBH4-MgH2 composite by ball milling, and the effect of catalysts on hydrogen storage properties of the modified LiBH4-MgH2 system was investigated. The experimental results show that LiBH4-MgH2 composite is a two-step dehydrogenation process, and Nb-based compounds can remarkably enhance its dehydrogenation kinetics. For the composite without addition of catalysts, the starting decomposition temperature for the first dehydrogenation step is around 320℃, and there is a long period of incubation time（around 220 min） for the occurrence of the second decomposition step even at high temperature of 450℃. It needs more than 10 h to complete the decomposition process and release around 9 wt% H2. After addition of 5 mol% NbF5, the starting decomposition temperature for the first dehydrogenation step is around 150℃, there is no incubation time for the second decomposition step, and it takes around 40 min to complete the second step and reaches a total dehydrogenation capacity of 9.5 wt%. NbF5 has better catalytic effect than NbC. Based on the hydrogenation/dehydrogenation behaviors and structural variation, the mechanism of catalytic effect was discussed.