La_（0.65）Mg_（0.35）Ni_x（x=3.0-3.5）储氢合金电极自放电性能的研究
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摘要
本文在绪论中综述了储氢合金的应用原理、研究发展与现状等,以储氢量较高的AB_(3.0-3.5)(新型RE-Mg-Ni系)储氢合金作为研究对象,较为系统地研究了A/B比和退火热处理对材料的结构特征、电化学性能以及自放电性能的影响。
通过中频感应熔炼制备了La_(0.65)Mg_(0.35)Ni_x(x=3.0-3.5)系列储氢电极合金。研究了合金的结构、电化学性能以及自放电性能。XRD研究表明,该系列合金主要由三相组成:LaNi_5相、(La,Mg)Ni_3相和(La,Mg)_2Ni_4相,随着x值的增大,LaNi_5相的丰度逐渐增加,(La,Mg)Ni_3相的丰度逐渐减少;最大放电容量从350.6mAh·g~(-1)(x=3.0)增加到351.2mAh·g_(-1)(x=3.1),然后逐渐减小到244.1mAh·g~(-1)(x=3.5);合金电极72h的荷电保持率从77.7%(x=3.0)增加到79.5%(x=3.1)然后逐渐减小到63.5%(x=3.5)。x=3.1的合金的荷电保持率最高,表明AB_(3-3.5)型La-Mg-Ni系储氢合金的A/B比对合金电极的自放电性能有较大的影响。
另一方面,研究了1173K热处理对该系储氢合金结构和性能的影响,并且对该系列合金电极的热处理前后进行对比。结果表明,热处理后的合金电极最大放电容量、循环稳定性、高倍率放电性能(HRD)、电极的自放电都有明显改善。
The application status,research and development of hydrogen storage alloy were comprehensively introduced in the first part of this paper.The new series of RE-Mg-Ni based AB_(3.0-3.5)-type alloys with PuNi_3-type structure had higher capacity than that of the AB_5-type alloys and thus were regarded as promising candidates for reversible hydrogen storage.In this work,the effect of the A/B ratio and annealing treatment on the structural,electrochemical properties and self-discharge property of the AB_(3.0-3.5)-type hydrogen storage alloys has been studied systematically.
The La_(0.65)Mg_(0.35)Ni_x(X=3.0-3.5) hydrogen storage alloys is prepared by induction melting.The structure,electrochemical properties and self-discharge property of as-cast alloys have been studied systematically by X-ray diffraction(XRD),scanning electron microscope(SEM) and electrochemical experiments.It is found by XRD analysis that all these alloys mainly consist of three phases:the LaNi_5 phase, (La,Mg)Ni_3 phase and(La,Mg)_2Ni_4 phase.The abundance of the LaNi_5 phase increases and that of La(La,Mg)Ni_3 phase decreases with increasing x.The electrochemical studies show that as x increases the maximum discharge capacity of the alloy electrodes first increases from 350.6mAh·g~(-1)(x=3.0)to 351.2mAh·g~(-1)(x=3.1)and then decreases to 244.1mAh·g~(-1)(x=3.5).Moreover,the capacity retention rate of 72h self-discharge increases from 77.7%(x=3.0)to 79.5%(x=3.1),and then decreases to 63.5%(x=3.5).When x=3.1,the capacity retention rate of alloy electrode is the maximum.
Besides,lectrochemical experiments show that the discharge capacity,high rate discharge performance,cycle stability and self-discharge property of the La_(0.35)Mg_(0.65)Ni_x(X=3.0-3.5) alloy electrodes were improved after annealing treatment at 1173K.
通过中频感应熔炼制备了La_(0.65)Mg_(0.35)Ni_x(x=3.0-3.5)系列储氢电极合金。研究了合金的结构、电化学性能以及自放电性能。XRD研究表明,该系列合金主要由三相组成:LaNi_5相、(La,Mg)Ni_3相和(La,Mg)_2Ni_4相,随着x值的增大,LaNi_5相的丰度逐渐增加,(La,Mg)Ni_3相的丰度逐渐减少;最大放电容量从350.6mAh·g~(-1)(x=3.0)增加到351.2mAh·g_(-1)(x=3.1),然后逐渐减小到244.1mAh·g~(-1)(x=3.5);合金电极72h的荷电保持率从77.7%(x=3.0)增加到79.5%(x=3.1)然后逐渐减小到63.5%(x=3.5)。x=3.1的合金的荷电保持率最高,表明AB_(3-3.5)型La-Mg-Ni系储氢合金的A/B比对合金电极的自放电性能有较大的影响。
另一方面,研究了1173K热处理对该系储氢合金结构和性能的影响,并且对该系列合金电极的热处理前后进行对比。结果表明,热处理后的合金电极最大放电容量、循环稳定性、高倍率放电性能(HRD)、电极的自放电都有明显改善。
The application status,research and development of hydrogen storage alloy were comprehensively introduced in the first part of this paper.The new series of RE-Mg-Ni based AB_(3.0-3.5)-type alloys with PuNi_3-type structure had higher capacity than that of the AB_5-type alloys and thus were regarded as promising candidates for reversible hydrogen storage.In this work,the effect of the A/B ratio and annealing treatment on the structural,electrochemical properties and self-discharge property of the AB_(3.0-3.5)-type hydrogen storage alloys has been studied systematically.
The La_(0.65)Mg_(0.35)Ni_x(X=3.0-3.5) hydrogen storage alloys is prepared by induction melting.The structure,electrochemical properties and self-discharge property of as-cast alloys have been studied systematically by X-ray diffraction(XRD),scanning electron microscope(SEM) and electrochemical experiments.It is found by XRD analysis that all these alloys mainly consist of three phases:the LaNi_5 phase, (La,Mg)Ni_3 phase and(La,Mg)_2Ni_4 phase.The abundance of the LaNi_5 phase increases and that of La(La,Mg)Ni_3 phase decreases with increasing x.The electrochemical studies show that as x increases the maximum discharge capacity of the alloy electrodes first increases from 350.6mAh·g~(-1)(x=3.0)to 351.2mAh·g~(-1)(x=3.1)and then decreases to 244.1mAh·g~(-1)(x=3.5).Moreover,the capacity retention rate of 72h self-discharge increases from 77.7%(x=3.0)to 79.5%(x=3.1),and then decreases to 63.5%(x=3.5).When x=3.1,the capacity retention rate of alloy electrode is the maximum.
Besides,lectrochemical experiments show that the discharge capacity,high rate discharge performance,cycle stability and self-discharge property of the La_(0.35)Mg_(0.65)Ni_x(X=3.0-3.5) alloy electrodes were improved after annealing treatment at 1173K.
引文
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