熔体快淬对AB_2型Laves相储氢电极合金循环寿命的影响

研究了快淬处理对 AB2 型 Laves 相电极合金循环稳定性的影响,用 XRD 和 SEM 分析了铸态及快淬态合金的相结构,并观察了合金的微观组织形貌。结果表明,快淬对 AB2 型贮氢合金循环稳定性的影响与合金的成分密切相关。快淬对 Ti 基电极合金的循环寿命有所提高,但不显著;对 Ti-Zr 基合金,随淬速增加,合金的循环稳定性急剧增加。快淬使 AB2 型电极合金循环寿命发生变化的根本原因是合金中形成了不同量的非晶相。

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.

Electrochemical hydrogen storage behaviors of as-cast and spun RE-Mg-Ni-Co-Al-based AB2-type alloys applied to Ni-MH battery

Preparation of La-Mg-Ni-Co-Al-based AB2-type alloys La0.8-xCe0.2YxMgNi3.4Co0.4Al0.1(x=0,0.05,0.10,0.15,0.20)was performed using melt spinning technology.The influences of spun rate and Y content on structures and electrochemical hydrogen storage characteristics were studied.The base phase LaMgNi4 and the lesser phase LaNis were detected by X-ray diffraction(XRD)and scanning electron microscope(SEM).The variations of spinning rate and Y content cause an obvious change in phase content,but without altering phase composition,namely,with spinning rate and Y content growing,LaMgNi4 phase content augments while LaNi5 content declines.Furthermore,melt spinning and the replacing La by Y refine the grains dramatically.The electrochemical tests show a favorable activation capability of the two kinds of alloys,and the maximum discharge capacities are achieved during the first cycle.Discharge capacity firstly increases and subsequently decreases with spinning rate rising,while cycle stability is ameliorated and discharge capacity decreases with Y addition increasing.It is found that the amelioration of cycle stability is due to the enhancement of anti-pulverization,anti-corrosion and antioxidation abilities by both replacement of La with Y and melt spinning.Moreover,with the increase of Y addition and/or spinning rate,the electrochemical kinetics that contain charge transfer rate,limiting current density(IL),hydrogen diffusion coefficient(D)and the high rate discharge ability(HRD)firstly augment and then reduce.

Structures and Electrochemical Performances of As-spun RE-Mg-Ni-Mn-based Alloys Applied to Ni-MH Battery

The La-Mg-Ni-Mn-based AB_2-type La_（1-x）Ce_xMgNi_（3.5）Mn_（0.5）（x = 0, 0.1, 0.2, 0.3, and 0.4） alloys were fabricated by melt spinning technology. The effects of Ce content on the structures and electrochemical hydrogen storage performances of the alloys were studied systematically. The XRD and SEM analyses proved that the experimental alloys consist of a major phase LaMgNi_4 and a secondary phase LaNi_5. The variation of Ce content causes an obvious change in the phase abundance of the alloys without changing the phase composition. Namely, with the increase of Ce content, the LaMgNi_4 phase augments and the LaNi_5 phase declines. The lattice constants and cell volumes of the alloys clearly shrink with increasing Ce content. Moreover, the Ce substitution for La results in the grains of the alloys clearly refined. The electrochemical tests showed that the substitution of Ce for La obviously improves the cycle stability of the as-spun alloys. The analyses on the capacity degradation mechanism demonstrate that the improvement can be attributed to the ameliorated anti-corrosion and antioxidation ability originating from substituting partial La with Ce. The as-spun alloys exhibit excellent activation capability, reaching the maximum discharge capacities just at the first cycling without any activation treatment. The substitution of Ce for La evidently improves the discharge potential characteristics of the as-spun alloys. The discharge capacity of the alloys first increases and then decreases with growing Ce content. Furthermore, a similar trend also exists in the electrochemical kinetics of the alloys, including the high rate discharge ability（HRD）, hydrogen diffusion coefficient（D）, limiting current density（IL） and charge transfer rate.

Structures and electrochemical performances of RE-Mg-Ni-Mn-based alloys prepared by casting and melt spinning

La-Mg-Ni-Mn-based AB2-type La（1–x）CexMgNi（3.5）Mn（0.5）（x=0–0.4） alloys were prepared by melt spinning technology. The detections of X-ray diffraction（XRD） and scanning electron microscopy（SEM） indicated that the experimental alloys consisted of a major phase LaMgNi4 and a secondary phase LaNi5. With spinning rate growing, the abundance of LaMgNi4 phase increased and that of LaNi5 phase decreased. Moreover, with the melt spinning rate increasing, both the lattice constants and cell volumes increased, and further accelerated the grains refinement of the alloys. The electrochemical tests showed that the as-spun alloys possessed excellent capability of activation, achieving the maximum discharge capacities just at the first cycling without any activation needed. As for the as-spun alloys, its discharge potential characteristics could be improved obviously by adopting the technology of melt spinning. In addition, the melt spinning raised electrochemical cycle stability of the alloys, the main reason was that the melt spinning enhanced the anti-pulverization ability of the alloys. With spinning rate increasing, the discharge capacity of the alloys presented a tendency to increase firstly then decrease. Moreover, the electrochemical kinetics of the alloys showed the same trend under fixed condition.

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.

Structures and electrochemical performances of as-spun RE-Mg-Ni-Co-Al 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 by melt spinning. The effects of Y content on the structures and electrochemical hydrogen storage characters were thoroughly studied. The structures of the experimental samples were analyzed by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. It is shown that there are a main phase LaMgNi4 and a second phase LaNi5 in the experimental samples. The variation of Y content incurs obvious changes of the phase abundance without changing phase composition. Namely, with the increase of Y content, the LaMgNi4 phase increases and LaNi5 phase decreases. Furthermore, melt spinning and the replacement of Y for La also lead to the grains refinement of the alloy. The electrochemical tests display that the as-spun alloys possess excellent activation properties, and obtain the maximums of discharge capacity at the first cycling. The replacement of Y for La can visibly facilitate the discharge potential characteristics, however,diminish the discharge capacity. The electrochemical kinetics, involving in the high rate discharge ability （HRD）, hydrogen diffusion coefficient （D）, limiting current density （IL） and charge transfer rate, increases firstly and then decreases with the increase of Y content. The cyclic stability is greatly improved by melt spinning and the replacement of Y for La, which is derived from the improvement of the anti-corrosion, oxidation-resistance and the anti-pulverization abilities.