Electrochemical hydrogen storage performance of as-cast and as-spun RE-Mg-Ni-Co-Al-based alloys applied to Ni/MH battery

The La-Mg-Ni-Co-Al-based AB2-type La0.8-xCe0.2YxMgNi3.4Co0.4Al0.1(x=0,0.05,0.1,0.15,0.2)alloys were prepared via melt spinning.The analyses of the X-ray diffraction(XRD)and scanning electron microscopy(SEM)proved that the experimental alloys contain the main phase LaMgNi4 and the second phase LaNi5.Increasing Y content and spinning rate lead to grain refinement and obvious change of the phase abundance without changing phase composition.Y substitution for La and melt spinning make the life-span of the alloys improved remarkably,which is attributed to the improvement of anti-oxidation,anti-pulverization and anti-corrosion abilities.In addition,the discharge capacity visibly decreases with increasing the Y content,while it firstly increases and then decreases with increasing spinning rate.The electrochemical kinetics increases to the optimum performance and then reduces with increasing spinning rate.Moreover,all the alloys achieve to the highest discharge capacities just at the initial cycle without activation.

Impacts of Melt Spinning and Element Substitution on Electrochemical Characteristics of the La–Mg–Ni-based A₂B₇-Type Alloys

The partial substitution of Zr for La has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni based A2B7-type electrode alloys. The melt spinning technology was used to prepare the La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x=0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The impacts of the melt spinning and the substituting La with Zr on the structures and the electrochemical hydrogen storage characteristics of the alloys were systemically investigated. The analysis of XRD and TEM reveals that the as-cast and spun alloys have a multiphase structure, composing of two main phases (La, Mg)2Ni7 and LaNi5 as well as a residual phase LaNi2. The electrochemical measurement indicates that both the substitution of Zr for La and the melt spinning ameliorate the electrochemical cycle stability of the alloys dramatically. Furthermore, the high rate discharge ability (HRD) of the as-spun (10 m/s) alloys notably declines with growing the amount of Zr substitution, while it first augments and then falls for the (x=0.1) alloy with rising the spinning rate.

Highly ameliorated gaseous and electrochemical hydrogen storage dynamics of nanocrystalline and amorphous LaMg_(12)-type alloys prepared by mechanical milling

Nanocrystalline and amorphous LaMg12-type alloy-Ni composites with a nominal composition of LaMg11Ni＋x wt.% Ni（x=100,200）were synthesized via ball milling.The influences of ball milling duration and Ni adding amount xon the gaseous and electrochemical hydrogen storage dynamics of the alloys were systematically studied.Gaseous hydrogen storage performances were studied by a differential scanning calorimeter and a Sievert apparatus.The dehydrogenation activation energy of the alloy hydrides was evaluated by Kissinger method.The electrochemical hydrogen storage dynamics of the alloys was investigated by an automatic galvanostatic system.The H atom diffusion and apparent activation enthalpy of the alloys were calculated.The results demonstrate that a variation in Ni content remarkably enhances the gaseous and electrochemical hydrogen storage dynamics performance of the alloys.The gaseous hydriding rate and high-rate discharge（HRD）ability of the alloys exhibit maximum values with varying milling duration.However,the dehydriding kinetics of the alloys is always accelerated by prolonging milling duration.Specifically,rising milling time from 5to 60 h makes the hydrogen desorption ratio（a ratio of the dehydrogenation amount in 20 min to the saturated hydrogenation amount）increase from 57%to 66%for x=100alloy and from 57%to 70%for x=200.Moreover,the improvement of gaseous hydrogen storage kinetics is attributed to the descending of dehydrogenation activation energy caused by the prolonging of milling duration and growing of Ni content.

Properties of Mechanically Milled Nanocrystalline and Amorphous Mg–Y–Ni Electrode Alloys for Ni–MH Batteries

Nanocrystalline and amorphous Mg2Ni-type Mg20-xYxNi10（x = 0,1,2,3 and 4） electrode alloys were fabricated using mechanical milling.The effects of the Y content and milling time on the microstructures and electrochemical performances of the alloys were investigated in detail.X-ray diffraction and transmission electron microscopy analyses revealed that the substitution of Y for Mg yields an obvious change in the phase composition and micro morphology of the alloys.When the Y content x ≤ 1,the substitution of Y for Mg does not change the major phase Mg2 Ni,but with a further increase in the Y content,the major phase of the alloys transforms into the YMg Ni4 YMg3 phase.A nanocrystalline and amorphous structure can be obtained by mechanical milling,and the amorphisation degree of the alloy visibly increases with increased milling time.Electrochemical measurements indicate that the discharge capacity of the alloys first increases and then decreases with increasing Y content and milling time.The substitution of Y for Mg dramatically ameliorates the cycle stability of the as-milled alloys,and the mechanical milling more or less impairs the cycle stability of the alloys.Furthermore,the high rate discharge ability,electrochemical impedance spectrum,Tafel polarisation curves and potential step measurements indicate that the electrochemical kinetic properties of the as-milled alloys first increase and then decrease with increasing Y content and milling time.

Structures and hydrogen storage properties of RE-Mg-Ni-Mn-based AB2-type alloys prepared by casting and melt spinning

To ameliorate the electrochemical hydrogen storage properties of RE-Mg-Ni-Mn-based AB2-type electrode alloys,La element was partially substituted by Ce,and La1-xCexMgNi3.5Mn0.5(x=0,0.1,0.2,0.3,0.4)alloys were fabricated by casting and melt spinning.The effects of Ce content on structures and electrochemical hydrogen storage properties of prepared alloys were studied in detail.Results show that the experimental alloys consist of LaMgNi4 and LaNi5 phases.The variation of Ce content,instead of changing phase composition,results in an obvious phase abundance change in the alloys,namely the amount of LaMgNi4 and LaNi5 phases,respectively,increases and decreases with Ce content growing.Moreover,the partial substitution of Ce for La leads to that the lattice keeps constant,cell volumes clearly decreases and the alloy grains are markedly refined.The electrochemical measurements reveal that the as-cast and as-spun alloys obtain the maximum discharge capacities at the first cycling without any activation needed.With Ce content increasing,the discharge capacity of as-cast alloys visibly decreases.By contrast,the as-spun alloys have the maximum discharge capacity value.The substitution of Ce for La dramatically promotes the cycle stability.Moreover,the electrochemical kinetic performances of as-cast and asspun alloys first increase and then decrease with Ce content increasing.

Structures and electrochemical performances of as-cast and spun RE-Mg-Ni-Mn-based alloys applied to Ni-MH battery

The RE-Mg-Ni-Mn-based AB2-type La（1-x）CexMgNi（3.5）Mn（0.5）（ x = 0- 0. 4） alloys were prepared by spinning treatment. For obtaining the optimum performance,the effects of Ce content and spinning rate on the hydrogen storage performance of the alloys were studied systematically. The results show that the variations of the spinning rate and Ce content result in noteworthy changes of the phase content without altering phase composition of the alloys. Specifically,the LaMgNi4 phase increases and LaNi5 phase decreases when increasing the spinning rate and Ce content. Furthermore,the crystalline grains of Cecontaining alloys prepared by spinning treatment are remarkably refined. The alloys own superior electrochemical performance. All alloys reach the optimal discharge capacity at the initial cycle. Increasing Ce content and spinning rate lead the discharge capacity and electrochemical kinetics rise to an optimal value and then start to reduce. Meanwhile,the electrochemical cycle stability is also improved,which is ascribed to the great enhancement of anti-pulverization and anti-corrosion abilities resulting from the spinning treatment and the substitution of Ce for La.

Structure and electrochemical characteristics of Mg–Ti–Ni-based electrode alloys synthesized by mechanical milling

The vacuum induction melting was adopted to fabricating Mg_(50−x)Ti_(x)Ni_(45)Al_(3)Co_(2)(x=0,1,2,3,4 at.%)composites protected by the high-purity helium atmosphere.Subsequently,the surface modification treatment of the as-cast alloys was carried out by mechanically coating nickel.The amorphous and nanocrystalline Mg_(50−x)Ti_(x)Ni_(45)Al_(3)Co_(2)(x=0–4)+50 wt.%Ni hydrogen storing alloys as the negative materials in batteries were prepared through ball milling,and the influences of milling time and Ti dosage on the structure and electrochemical hydrogen storing behaviors of the corresponding samples were studied in detail.The electrochemical testing reveals that the as-milled alloys have excellent performances and can finish the electrochemical hydrogenation and dehydrogenation at indoor temperature.In the first cycle without activation,the ball milling alloy obtains the maximum value of discharge capacity.Discharge capacity and cyclic steadiness of the composites conspicuously grow as Ti content and milling duration increase.Concretely,the capacity retaining rate at 100th cycle and the discharge capacity of 30 h milling samples augment from 53%to 78%and from 435.2 to 567.2 mAh/g with changing Ti content from 0 to 4.The same performances of the alloy(x=4)are enhanced from 61%to 78%and from 379.9 to 567.2 mAh/g,respectively,with extending milling duration.Moreover,high rate discharge ability,potential-step measurements,potentiodynamic polarization curves and electrochemical impedance spectrum manifest that the electrochemical kinetics properties can achieve significant amelioration as Ti content varies and milling duration is extended.