At present,there is limited research on the application of fuel cell power generation system technology using solid hydrogen storage materials,especially in hydrogen-assisted two-wheelers.Considering the disadvantages...At present,there is limited research on the application of fuel cell power generation system technology using solid hydrogen storage materials,especially in hydrogen-assisted two-wheelers.Considering the disadvantages of low hydrogen storage capacity and poor kinetics of hydrogen storage materials,our primary focus is to achieve smooth hydrogen ab-/desorption over a wide temperature range to meet the requirements of fuel cells and their integrated power generation systems.In this paper,the Ti_(0.9)Zr_(0.1)Mn_(1.45)V_(0.4)Fe_(0.15) hydrogen storage alloy was successfully prepared by arc melting.The maximum hydrogen storage capacity reaches 1.89 wt% at 318 K.The alloy has the capability to absorb 90% of hydrogen storage capacity within 50 s at 7 MPa and release 90% of hydrogen within 220 s.Comsol Multiphysics 6.0 software was used to simulate the hydrogen ab-/desorption processes of the tank.The flow rate of cooling water during hydrogen absorption varied in a gradient of(0.02 t x)m s^(-1)(x=0,0.02,0.04,0.06,0.08,0.1,0.12).Cooling water flow rate is positively correlated with the hydrogen absorption rate but negatively correlated with the cost.When the cooling rate is 0.06 m s^(-1),both simulation and experimentation have shown that the hydrogen storage tank is capable of steady hydrogen desorption for over 6 h at a flow rate of 2 L min^(-1).Based on the above conclusions,we have successfully developed a hydrogen-assisted two-wheeler with a range of 80 km and achieved regional demonstration operations in Changzhou and Shaoguan.This paper highlights the achievements of our team in the technological development of fuel cell power generation systems using solid hydrogen storage materials as hydrogen storage carriers and their application in twowheelers in recent years.展开更多
In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system （AB3.5-type） hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（x=0...In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system （AB3.5-type） hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（x=0, 0.10, 0.15, 0.2） hydrogen storage alloys were prepared. X-ray diffraction （XRD）, scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS） analyses revealed that two alloys （x=0.0 and 0.10） were composed of （La,Mg）2（Ni,Al）7 phase, La（Ni,A1）5 phase and （La,Mg）Ni2 phase, while other alloys （x=0.15 and 0.20） consisted of （La,Mg）2（Ni,A1）7 phase, La（Ni,A1）5 phase, （La,Mg）Ni2 phase and （La,Mg）（Ni,A1）3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Electrochemical studies showed that the discharge capacity decreased from 360 mAh/g （x=-0.00） to 335 mAh/g （x=-0.20） as x increased. But the high-rate dischargeability （HRD） of alloy electrodes increased from 26% （x=0.00） to 56% （x=-0.20） at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.展开更多
The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox （x = 0, 0.1, 0.2, 0.3, 0.4） alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD,...The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox （x = 0, 0.1, 0.2, 0.3, 0.4） alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Co- ffee alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient （D） along with the limiting current density （IL） and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.展开更多
A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The...A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showed that the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis without any activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp (0.1 MPa)=-3026/T+5.814 (523 K≤T≤623 K) for hydriding and Igp (0.1 MPa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1-a)]3/2 = kt and the apparent activation energy for the nucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31kJ/(mol.H2) and 59.9±2.99kJ/(mol.H2)respectively.展开更多
In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of th...In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x>0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA·h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.展开更多
The influence of the addition of Cu(OH)2 to 6 mol/L KOH alkaline electrolyte on the electrochemical properties of La2Mg0.9Al0.1Ni7.5Co1.5 hydrogen storage alloy electrode was investigated by electron probe X-ray micro...The influence of the addition of Cu(OH)2 to 6 mol/L KOH alkaline electrolyte on the electrochemical properties of La2Mg0.9Al0.1Ni7.5Co1.5 hydrogen storage alloy electrode was investigated by electron probe X-ray microanalysis(EPMA),X-ray diffraction(XRD) and electrochemical measurements. EPMA micrographs and XRD patterns show that the surface of the hydride electrode is plated by metal copper film. The thickness and compactness of Cu film increase with the increment of charge-discharge cycle number. The copper film of the hydride electrode surface can keep the hydrogen storage alloy particle in the electrode interior from oxidizing availably. The addition of Cu(OH)2 to alkaline electrolyte lowers the activation property and the high rate dischargeability of the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrode,but has no negative effect on the maximum discharge capacity of the hydride electrode. Moreover,it is effective to improve the cyclic stability of the hydride electrode utilizing electrodeposit Cu film on the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrodes surface.展开更多
Structural analysis was made using X-ray diffraction (XRD) Rietveld refinement on a series of La1+xMg2-xNi9 (x=0.0-1.0) ternary alloys. Results showed that each of La1+xMg2-xNi9 alloys was a PuNi3-type structure stack...Structural analysis was made using X-ray diffraction (XRD) Rietveld refinement on a series of La1+xMg2-xNi9 (x=0.0-1.0) ternary alloys. Results showed that each of La1+xMg2-xNi9 alloys was a PuNi3-type structure stacked by LaNi5 and (La, Mg) Ni2 blocks. Electrochemical tests revealed that discharge abilities of these La-Mg-Ni ternary alloys mainly depended on their atomic distances between (La, Mg) and Ni, which could be modified by varying the atomic ratios of La/Mg.展开更多
In order to improve the gaseous and electrochemical hydrogen storage kinetics of the M2Nitype alloy, the elements Cu and Nd were added in the alloy. The nanocrystalline and amorphous Mg2Ni-type alloys with the composi...In order to improve the gaseous and electrochemical hydrogen storage kinetics of the M2Nitype alloy, the elements Cu and Nd were added in the alloy. The nanocrystalline and amorphous Mg2Ni-type alloys with the composition of（Mg24Ni10Cu2）100-xNdx（x = 0, 5, 10, 15, 20） were prepared by melt spinning technology. The effects of Nd content on the structures and hydrogen storage kinetics of the alloys were investigated. The characterization by X-ray diffraction（XRD）, transmission electron microscopy（TEM） and scanning electron microscopy（SEM） reveals that all the as-cast alloys hold multiphase structures, containing Mg2Ni-type major phase as well as some secondary phases Mg6Ni, Nd5Mg41, and Nd Ni, whose amounts clearly grow with increasing Nd content. Furthermore, the as-spun Nd-free alloy displays an entire nanocrystalline structure, whereas the as-spun Nd-added alloys hold a mixed structure of nanocrystalline and amorphous structure and the amorphization degree of the alloys visibly increases with the rising of the Nd content, suggesting that the addition of Nd facilitates the glass forming in the Mg2Ni-type alloy. The measurement of the hydrogen storage kinetics indicates that the addition of Nd significantly improves the gaseous and electrochemical hydrogen storage kinetics of the alloys. The addition of Nd enhances the diffusion ability of hydrogen atoms in the alloy, but it impairs the charge-transfer reaction on the surface of the alloy electrode, which makes the high rate discharge ability（HRD） of the alloy electrode fi rst mount up and then go down with the growing of Nd content.展开更多
MgH_(2)with a large hydrogen capacity is regarded as a promising hydrogen storage material.However,it still suffers from high thermal stability and sluggish kinetics.In this paper,highly dispersed nano-Ni has been suc...MgH_(2)with a large hydrogen capacity is regarded as a promising hydrogen storage material.However,it still suffers from high thermal stability and sluggish kinetics.In this paper,highly dispersed nano-Ni has been successfully prepared by using the polyol reduction method with an average size of 2.14 nm,which significantly improves the de/rehydrogenation properties of MgH_(2).The MgH_(2)–10wt%nano-Ni sample starts releasing H_(2)at 497 K,and roughly 6.2wt%H_(2)has been liberated at 583 K.The rehydrogenation kinetics of the sample are also greatly improved,and the adsorption capacity reaches 5.3wt%H_(2)in 1000 s at 482 K and under 3 MPa hydrogen pressure.Moreover,the activation energies of de/rehydrogenation of the MgH_(2)–10wt%nano-Ni sample are reduced to(88±2)and(87±1)kJ·mol−1,respectively.In addition,the thermal stability of the MgH_(2)–10wt%nano-Ni system is reduced by 5.5 kJ per mol H_(2)from that of pristine MgH_(2).This finding indicates that nano-Ni significantly improves both the thermodynamic and kinetic performances of the de/rehydrogenation of MgH_(2),serving as a bi-functional additive of both reagent and catalyst.展开更多
Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is ...Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.展开更多
The effect of Mn substitution on phase structure, hydrogen hydriding/dehydriding properties (plateau pressure and slope) and reaction heat enthalpy of LaNi4.25-xAl0.75Mnx alloys (x=0, 0.25, 0.35, 0.45, 0.55 and 0.65) ...The effect of Mn substitution on phase structure, hydrogen hydriding/dehydriding properties (plateau pressure and slope) and reaction heat enthalpy of LaNi4.25-xAl0.75Mnx alloys (x=0, 0.25, 0.35, 0.45, 0.55 and 0.65) were studied. The experimental results show that all LaNi4.25-xAl0.75Mnx alloys have single phase and have the same hexagonal structure as that of LaNi5 alloy (CaCu5 type, P6/mmm). With increasing Mn substitution content, the cell parameters of LaNi4.25-xAl0.75Mnx alloy greatly increase, but the maximum hydrogen storage capacity and the equilibrium absorption pressure of LaNi4.25-xAl0.75Mnx alloy decrease from 1.38 wt.% to 1.18 wt.% and from 1.61 to 0.0712 MPa, respectively. Moreover, the hydrogen pressure plateau slope factor σ increases from 0.014 to 0.18, but the hysteresis factor is nearly constant. The heat enthalpy absolute value |ΔHplat| increases from 46.7 kJ·mol-1 H2 to 56.1 kJ·mol-1 H2 as the Mn content x increases from 0 to 0.65.展开更多
The annealing treatment was found to improve the cyclic stability but to degmde discharpe capacity, activation and high-rate discharpeability for the Ti-substituted AB2type alloy electrode. A larper polarization was f...The annealing treatment was found to improve the cyclic stability but to degmde discharpe capacity, activation and high-rate discharpeability for the Ti-substituted AB2type alloy electrode. A larper polarization was found in the annealed alloy because of its poor discharpe kinetics resulted hem the structural homogeneity. At larae discharpe cumnts, the hydmpen dchsion in the bulk of the alloy was mpaofed as the mte-determining step. Based on the P ressure-composition isotherm measurement, we concluded that the decrease in discharpeability of the annealed alloy is owing to the low and flat pressure plateau, as well as the large hysteresis, but the hydrgen stomge density almost remains unchangeable after annealing.展开更多
A partial substitution of Ni by Cu has been carried out in order to improve the hydrogen storage characteristics of the Mg2Ni-type alloys. The nanocrystalline Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) alloys are synthesized b...A partial substitution of Ni by Cu has been carried out in order to improve the hydrogen storage characteristics of the Mg2Ni-type alloys. The nanocrystalline Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) alloys are synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM). The electrochemical performances were evaluated by an automatic galvanostatic system. The hydrogen absorption and desorption kinetics of the alloys were determined by using an automatically controlled Sieverts apparatus. The results indicate that the substitution of Cu for Ni does not alter the major phase Mg2Ni. The Cu substitution significantly ameliorates the electrochemical hydrogen storage performances of alloys, involving both the discharge capacity and the cycle stability. The hydrogen absorption capacity of alloys has been observed to be first increase and then decrease with an increase in the Cu contents. However, the hydrogen desorption capacity of the alloys exhibit a monotonous growth with an increase in the Cu contents.展开更多
In ordertoimprovethe dischargecapacity of Ti2 Ni hydrogen storage alloy, the phases and effecton the property for Ti Nialloy with alittle La( La contentisbetween 5 25 wt% and12 62 wt%) were investigated in this pa...In ordertoimprovethe dischargecapacity of Ti2 Ni hydrogen storage alloy, the phases and effecton the property for Ti Nialloy with alittle La( La contentisbetween 5 25 wt% and12 62 wt%) were investigated in this paper. It is found that La exists in the form ofLaNi5 ,thesecond phase,in Ti Nialloy when La> 8 wt% . LaNi5 phasecaneffectivelyim provethe activity property and discharge capacity of Ti Ni alloy. While the soluble Ti inmain phase Ti2 Niisadverseto hydrogen adsorption desorption cycle and itshould be dimin ished .展开更多
The effects of low-Co AB_5 type hydrogen storage alloys prepared by quenchingand annealing on the performances of MH-Ni batteries were investigated, and the characteristics ofthe low-Co AB_5 type hydrogen storage allo...The effects of low-Co AB_5 type hydrogen storage alloys prepared by quenchingand annealing on the performances of MH-Ni batteries were investigated, and the characteristics ofthe low-Co AB_5 type hydrogen storage alloys were compared with those of the high-Co AB_5 typehydrogen storage alloy as well. The results showed that the faster the cooling of the low-Cohydrogen storage alloy is, the better homogeneity of the chemical composition for the alloy and thelonger cycle life of the battery are, but the electrochemical discharge capacity and high-ratedischarge ability are reduced. The high-rate discharge ability and charge retention of MH-Nibatteries for the conventional as-cast annealed low-Co hydrogen storage alloy were superior to thosefor the rapidly quenched low-Co hydrogen storage alloy and the high-Co hydrogen storage alloy, buta little inferior in the cycle life.展开更多
(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capaciti...(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capacities of the synthesized alloys were measured. Non-hygroscopic LaNiO;phase formed during sintering（at 1200 °C for 2 h） as a result of the reaction of hygroscopic La;O;with NiO. Another sinter product was Mg;Ni;O phase. Both mixed oxide sinter products facilitated the La-Ni and Mg-Ni phase formations. X-ray diffraction peaks indicated that the first stable phase appeared in the alloy structure was LaNi;which formed upon reduction of La;NiO;phase. Increase in Mg content caused formation of La;Mg;Ni;phase in the alloy structure and the presence of this phase improved the hydrogen storage performance of the electrodes. It was observed that(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys have promising discharge capacities change between 319 m Ah/g and 379 m Ah/g depending on the alloy Mg content.展开更多
基金financed by the National Key Research and Development Program of China[grants number 2022YFB3803800]the National Natural Science Foundation of China[grants number 52071141,52271212,52201250,51771056]Interdisciplinary Innovation Program of North China Electric Power University[grants number XM2112355].
文摘At present,there is limited research on the application of fuel cell power generation system technology using solid hydrogen storage materials,especially in hydrogen-assisted two-wheelers.Considering the disadvantages of low hydrogen storage capacity and poor kinetics of hydrogen storage materials,our primary focus is to achieve smooth hydrogen ab-/desorption over a wide temperature range to meet the requirements of fuel cells and their integrated power generation systems.In this paper,the Ti_(0.9)Zr_(0.1)Mn_(1.45)V_(0.4)Fe_(0.15) hydrogen storage alloy was successfully prepared by arc melting.The maximum hydrogen storage capacity reaches 1.89 wt% at 318 K.The alloy has the capability to absorb 90% of hydrogen storage capacity within 50 s at 7 MPa and release 90% of hydrogen within 220 s.Comsol Multiphysics 6.0 software was used to simulate the hydrogen ab-/desorption processes of the tank.The flow rate of cooling water during hydrogen absorption varied in a gradient of(0.02 t x)m s^(-1)(x=0,0.02,0.04,0.06,0.08,0.1,0.12).Cooling water flow rate is positively correlated with the hydrogen absorption rate but negatively correlated with the cost.When the cooling rate is 0.06 m s^(-1),both simulation and experimentation have shown that the hydrogen storage tank is capable of steady hydrogen desorption for over 6 h at a flow rate of 2 L min^(-1).Based on the above conclusions,we have successfully developed a hydrogen-assisted two-wheeler with a range of 80 km and achieved regional demonstration operations in Changzhou and Shaoguan.This paper highlights the achievements of our team in the technological development of fuel cell power generation systems using solid hydrogen storage materials as hydrogen storage carriers and their application in twowheelers in recent years.
基金supported by the Key Projects in International Science and Technology Cooperation from Ministry of Science and Technology of the PRC (2006DFB52550, 2007DFA51020)the National Natural Science Foundation of China (20363001)
文摘In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system （AB3.5-type） hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（x=0, 0.10, 0.15, 0.2） hydrogen storage alloys were prepared. X-ray diffraction （XRD）, scanning electron microscopy （SEM） and energy dispersive spectrometer （EDS） analyses revealed that two alloys （x=0.0 and 0.10） were composed of （La,Mg）2（Ni,Al）7 phase, La（Ni,A1）5 phase and （La,Mg）Ni2 phase, while other alloys （x=0.15 and 0.20） consisted of （La,Mg）2（Ni,A1）7 phase, La（Ni,A1）5 phase, （La,Mg）Ni2 phase and （La,Mg）（Ni,A1）3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Electrochemical studies showed that the discharge capacity decreased from 360 mAh/g （x=-0.00） to 335 mAh/g （x=-0.20） as x increased. But the high-rate dischargeability （HRD） of alloy electrodes increased from 26% （x=0.00） to 56% （x=-0.20） at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.
基金Funded by National Natural Science Foundations of China(Nos.51161015 and 50961009)Natural Science Foundation of Inner Mongolia,China(Nos.2011ZD10 and 2010ZD05)Higher Education Science Research Project of Inner Mongolia,China(No.NJzy08071)
文摘The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox （x = 0, 0.1, 0.2, 0.3, 0.4） alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Co- ffee alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient （D） along with the limiting current density （IL） and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.
文摘A high activity and large capacity of hydrogen storage alloy Mg2Ni by hydriding combustion synthesis was investigated by means of pressure composition isotherms, X-ray diffraction and scanning electron microscopy. The results showed that the maximum hydrogen absorption capacity of Mg2Ni is 3.25 mass fraction at 523 K, just after synthesis without any activation. The relationships between the equilibrium plateau pressure and the temperature for Mg2Ni were lgp (0.1 MPa)=-3026/T+5.814 (523 K≤T≤623 K) for hydriding and Igp (0.1 MPa)=-3613/T+6.715 (523 K≤T ≤623 K) for dehydriding. The kinetic equation is [-ln(1-a)]3/2 = kt and the apparent activation energy for the nucleation and growth-controlled hydrogen absorption and desorption were determined to be 64.3±2.31kJ/(mol.H2) and 59.9±2.99kJ/(mol.H2)respectively.
基金Project(2006AA05Z132) supported by High-tech Research and Development Program of ChinaProject(50642033) supported by the National Natural Science Foundation of China+1 种基金Project(200711020703) supported by the Natural Science Foundation of Inner Mongolia, ChinaProject (20050205) supported by Science and Technology Planned Project of Inner Mongolia, China
文摘In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x>0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA·h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.
基金Project(50171021) supported by the National Natural Science Foundation of China
文摘The influence of the addition of Cu(OH)2 to 6 mol/L KOH alkaline electrolyte on the electrochemical properties of La2Mg0.9Al0.1Ni7.5Co1.5 hydrogen storage alloy electrode was investigated by electron probe X-ray microanalysis(EPMA),X-ray diffraction(XRD) and electrochemical measurements. EPMA micrographs and XRD patterns show that the surface of the hydride electrode is plated by metal copper film. The thickness and compactness of Cu film increase with the increment of charge-discharge cycle number. The copper film of the hydride electrode surface can keep the hydrogen storage alloy particle in the electrode interior from oxidizing availably. The addition of Cu(OH)2 to alkaline electrolyte lowers the activation property and the high rate dischargeability of the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrode,but has no negative effect on the maximum discharge capacity of the hydride electrode. Moreover,it is effective to improve the cyclic stability of the hydride electrode utilizing electrodeposit Cu film on the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrodes surface.
基金This work was supported by the National Natural Science Foundation of China under grant No.50071052 and No.50131040.
文摘Structural analysis was made using X-ray diffraction (XRD) Rietveld refinement on a series of La1+xMg2-xNi9 (x=0.0-1.0) ternary alloys. Results showed that each of La1+xMg2-xNi9 alloys was a PuNi3-type structure stacked by LaNi5 and (La, Mg) Ni2 blocks. Electrochemical tests revealed that discharge abilities of these La-Mg-Ni ternary alloys mainly depended on their atomic distances between (La, Mg) and Ni, which could be modified by varying the atomic ratios of La/Mg.
基金Funded by the National Natural Science Foundations of China(Nos.51161015 and 51371094)
文摘In order to improve the gaseous and electrochemical hydrogen storage kinetics of the M2Nitype alloy, the elements Cu and Nd were added in the alloy. The nanocrystalline and amorphous Mg2Ni-type alloys with the composition of（Mg24Ni10Cu2）100-xNdx（x = 0, 5, 10, 15, 20） were prepared by melt spinning technology. The effects of Nd content on the structures and hydrogen storage kinetics of the alloys were investigated. The characterization by X-ray diffraction（XRD）, transmission electron microscopy（TEM） and scanning electron microscopy（SEM） reveals that all the as-cast alloys hold multiphase structures, containing Mg2Ni-type major phase as well as some secondary phases Mg6Ni, Nd5Mg41, and Nd Ni, whose amounts clearly grow with increasing Nd content. Furthermore, the as-spun Nd-free alloy displays an entire nanocrystalline structure, whereas the as-spun Nd-added alloys hold a mixed structure of nanocrystalline and amorphous structure and the amorphization degree of the alloys visibly increases with the rising of the Nd content, suggesting that the addition of Nd facilitates the glass forming in the Mg2Ni-type alloy. The measurement of the hydrogen storage kinetics indicates that the addition of Nd significantly improves the gaseous and electrochemical hydrogen storage kinetics of the alloys. The addition of Nd enhances the diffusion ability of hydrogen atoms in the alloy, but it impairs the charge-transfer reaction on the surface of the alloy electrode, which makes the high rate discharge ability（HRD） of the alloy electrode fi rst mount up and then go down with the growing of Nd content.
基金financially supported by the National Natural Science Foundation of China (No. 52071177)the Natural Science Foundation of Guangxi, China (No. 2020GXNSFAA297074)+1 种基金the Jiangsu Key Laboratory for Advanced Metallic Materials (No. BM2007204)the Guangxi Key Laboratory of Information Materials (No. 211021-K)
文摘MgH_(2)with a large hydrogen capacity is regarded as a promising hydrogen storage material.However,it still suffers from high thermal stability and sluggish kinetics.In this paper,highly dispersed nano-Ni has been successfully prepared by using the polyol reduction method with an average size of 2.14 nm,which significantly improves the de/rehydrogenation properties of MgH_(2).The MgH_(2)–10wt%nano-Ni sample starts releasing H_(2)at 497 K,and roughly 6.2wt%H_(2)has been liberated at 583 K.The rehydrogenation kinetics of the sample are also greatly improved,and the adsorption capacity reaches 5.3wt%H_(2)in 1000 s at 482 K and under 3 MPa hydrogen pressure.Moreover,the activation energies of de/rehydrogenation of the MgH_(2)–10wt%nano-Ni sample are reduced to(88±2)and(87±1)kJ·mol−1,respectively.In addition,the thermal stability of the MgH_(2)–10wt%nano-Ni system is reduced by 5.5 kJ per mol H_(2)from that of pristine MgH_(2).This finding indicates that nano-Ni significantly improves both the thermodynamic and kinetic performances of the de/rehydrogenation of MgH_(2),serving as a bi-functional additive of both reagent and catalyst.
文摘Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.
文摘The effect of Mn substitution on phase structure, hydrogen hydriding/dehydriding properties (plateau pressure and slope) and reaction heat enthalpy of LaNi4.25-xAl0.75Mnx alloys (x=0, 0.25, 0.35, 0.45, 0.55 and 0.65) were studied. The experimental results show that all LaNi4.25-xAl0.75Mnx alloys have single phase and have the same hexagonal structure as that of LaNi5 alloy (CaCu5 type, P6/mmm). With increasing Mn substitution content, the cell parameters of LaNi4.25-xAl0.75Mnx alloy greatly increase, but the maximum hydrogen storage capacity and the equilibrium absorption pressure of LaNi4.25-xAl0.75Mnx alloy decrease from 1.38 wt.% to 1.18 wt.% and from 1.61 to 0.0712 MPa, respectively. Moreover, the hydrogen pressure plateau slope factor σ increases from 0.014 to 0.18, but the hysteresis factor is nearly constant. The heat enthalpy absolute value |ΔHplat| increases from 46.7 kJ·mol-1 H2 to 56.1 kJ·mol-1 H2 as the Mn content x increases from 0 to 0.65.
文摘The annealing treatment was found to improve the cyclic stability but to degmde discharpe capacity, activation and high-rate discharpeability for the Ti-substituted AB2type alloy electrode. A larper polarization was found in the annealed alloy because of its poor discharpe kinetics resulted hem the structural homogeneity. At larae discharpe cumnts, the hydmpen dchsion in the bulk of the alloy was mpaofed as the mte-determining step. Based on the P ressure-composition isotherm measurement, we concluded that the decrease in discharpeability of the annealed alloy is owing to the low and flat pressure plateau, as well as the large hysteresis, but the hydrgen stomge density almost remains unchangeable after annealing.
文摘A partial substitution of Ni by Cu has been carried out in order to improve the hydrogen storage characteristics of the Mg2Ni-type alloys. The nanocrystalline Mg20Ni10-xCux (x = 0, 1, 2, 3, 4) alloys are synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM). The electrochemical performances were evaluated by an automatic galvanostatic system. The hydrogen absorption and desorption kinetics of the alloys were determined by using an automatically controlled Sieverts apparatus. The results indicate that the substitution of Cu for Ni does not alter the major phase Mg2Ni. The Cu substitution significantly ameliorates the electrochemical hydrogen storage performances of alloys, involving both the discharge capacity and the cycle stability. The hydrogen absorption capacity of alloys has been observed to be first increase and then decrease with an increase in the Cu contents. However, the hydrogen desorption capacity of the alloys exhibit a monotonous growth with an increase in the Cu contents.
文摘In ordertoimprovethe dischargecapacity of Ti2 Ni hydrogen storage alloy, the phases and effecton the property for Ti Nialloy with alittle La( La contentisbetween 5 25 wt% and12 62 wt%) were investigated in this paper. It is found that La exists in the form ofLaNi5 ,thesecond phase,in Ti Nialloy when La> 8 wt% . LaNi5 phasecaneffectivelyim provethe activity property and discharge capacity of Ti Ni alloy. While the soluble Ti inmain phase Ti2 Niisadverseto hydrogen adsorption desorption cycle and itshould be dimin ished .
文摘The effects of low-Co AB_5 type hydrogen storage alloys prepared by quenchingand annealing on the performances of MH-Ni batteries were investigated, and the characteristics ofthe low-Co AB_5 type hydrogen storage alloys were compared with those of the high-Co AB_5 typehydrogen storage alloy as well. The results showed that the faster the cooling of the low-Cohydrogen storage alloy is, the better homogeneity of the chemical composition for the alloy and thelonger cycle life of the battery are, but the electrochemical discharge capacity and high-ratedischarge ability are reduced. The high-rate discharge ability and charge retention of MH-Nibatteries for the conventional as-cast annealed low-Co hydrogen storage alloy were superior to thosefor the rapidly quenched low-Co hydrogen storage alloy and the high-Co hydrogen storage alloy, buta little inferior in the cycle life.
基金Financial assistance from The Scientific and Technological Research Council of Turkey is gratefully acknowledged(Project No:MAG 113M139)
文摘(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys were synthesized from the sintered mixture of La;O;+ Ni O + Co O + Mg O in the molten CaCl;electrolyte at 750 °C and the electrochemical hydrogen storage capacities of the synthesized alloys were measured. Non-hygroscopic LaNiO;phase formed during sintering（at 1200 °C for 2 h） as a result of the reaction of hygroscopic La;O;with NiO. Another sinter product was Mg;Ni;O phase. Both mixed oxide sinter products facilitated the La-Ni and Mg-Ni phase formations. X-ray diffraction peaks indicated that the first stable phase appeared in the alloy structure was LaNi;which formed upon reduction of La;NiO;phase. Increase in Mg content caused formation of La;Mg;Ni;phase in the alloy structure and the presence of this phase improved the hydrogen storage performance of the electrodes. It was observed that(La;Mg;);(Ni;Co;);（x = 0.125, 0.25, 0.5） alloys have promising discharge capacities change between 319 m Ah/g and 379 m Ah/g depending on the alloy Mg content.
