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Article(id=1241081032800268435, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, articleNumber=null, orderNo=null, doi=10.3969/j.issn.0253-6099.2024.04.017, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1709481600000, receivedDateStr=2024-03-04, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773826376390, onlineDateStr=2026-03-18, pubDate=1722441600000, pubDateStr=2024-08-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773826376390, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773826376390, creator=13701087609, updateTime=1773826376390, updator=13701087609, issue=Issue{id=1241081025531540408, tenantId=1146029695717560320, journalId=1235980550691926019, year='2024', volume='44', issue='4', pageStart='1', pageEnd='258', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773826374657, creator=13701087609, updateTime=1773827517159, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241085817590960730, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241085817590960731, tenantId=1146029695717560320, journalId=1235980550691926019, issueId=1241081025531540408, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=90, endPage=94, ext={EN=ArticleExt(id=1241081033618157753, articleId=1241081032800268435, tenantId=1146029695717560320, journalId=1235980550691926019, language=EN, title=Element Substitution and Electrochemical Performance of La-Mg-Ni Based Hydrogen Storage Alloys for Automotive Batteries, columnId=1241081026567533498, journalTitle=Mining and Metallurgical Engineering, columnName=SPECIAL ISSUE: BATTERY MATERIALS, runingTitle=null, highlight=null, articleAbstract=

A kind of hydrogen storage alloy of La0.7R0.1Mg0.2Ni3.35Al0.15 (R=La/Nd/Sm) was synthesized with induction melting method, and the effect of La substituted with rare earth element Nd/Sm on the phase structure, microstructure, and electrochemical performance of the hydrogen storage alloy was explored. The results show that the substitution of Nd or Sm for La doesn't change the phase composition of the hydrogen storage alloy, which is still composed of LaNi5, (LaMg)2Ni7, and (LaMg)5Ni19 phases, but leads to higher abundance of LaNi5 and (LaMg)5Ni19 phases, and lower abundance of (LaMg)2Ni7 phase in the hydrogen storage alloy. The hydrogen storage alloy, with La, Nd and Sm as R, deliver the maximum discharge capacities of 377 mAh/g, 382 mAh/g and 376 mAh/g, respectively, after the second charge-discharge cycle. With La substituted with Nd or Sm, the hydrogen storage alloy has its high-rate discharge capacity, the charge retention rate after 24 hours, and capacity retention rate after 100 cycles all improved to some extent, among which the hydrogen storage alloy with Nd as R is the best in all corresponding performance. Moreover, the substitution of La with Nd or Sm can make the hydrogen storage alloy with higher exchange current density and higher coefficient of hydrogen diffusion. Its high-rate discharge performance, exchange current density and hydrogen diffusion coefficient are all in in the same trend, indicating that high-rate discharge performance of the hydrogen storage depends on both exchange current density and hydrogen diffusion coefficient.

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采用感应熔炼方法制备了La0.7R0.1Mg0.2Ni3.35Al0.15（R=La/Nd/Sm）储氢合金，研究了稀土元素Nd/Sm替代La对储氢合金相结构和电化学性能的影响。结果表明，采用Nd或Sm替代La时，储氢合金物相组成未发生改变，仍由LaNi5、（LaMg）2Ni7和（LaMg）5Ni19相组成，但储氢合金中LaNi5相和（LaMg）5Ni19相丰度会增加、（LaMg）2Ni7相丰度减小。R为La、Nd和Sm时储氢合金的最大放电比容量均在第2次充放电循环时获得，分别为377 mAh/g、382 mAh/g和376 mAh/g；采用Nd或Sm替代La，储氢合金高倍率放电性能、24 h荷电保持率和充放电循环100次时的容量保持率都不同程度地增加，且R为Nd时储氢合金的相应值最大。采用Nd或Sm替代La会使得储氢合金的交换电流密度、氢扩散系数增加，储氢合金电极的高倍率放电性能与交换电流密度和氢扩散系数变化趋势一致，表明储氢合金电极的高倍率放电性能由交换电流密度和氢扩散系数共同决定。

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王飞（1979—），男，河北张家口人，硕士，副教授，主要研究方向为汽车电池。E-mail：

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王飞（1979—），男，河北张家口人，硕士，副教授，主要研究方向为汽车电池。E-mail：

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王飞（1979—），男，河北张家口人，硕士，副教授，主要研究方向为汽车电池。E-mail：

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（a）R=La；（b）R=Nd；（c）R=Sm

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（a）线性极化曲线；（b）电化学阻抗谱

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R相结构相组成晶格参数相丰度/%
a/nmc/nm
LaCaCu5LaNi50.504 90.402 64
Ce2Ni7（LaMg）2Ni70.505 22.432 876
Pr5Co19（LaMg）5Ni190.505 83.237 36
Ce5Co190.505 54.855 814
NdCaCu5LaNi50.504 30.401 743
Ce2Ni7（LaMg）2Ni70.505 12.434 232
Pr5Co19（LaMg）5Ni190.504 63.246 94
Ce5Co190.504 54.851 421
SmCaCu5LaNi50.504 30.404 328
Ce2Ni7（LaMg）2Ni70.505 52.433 635
Pr5Co19（LaMg）5Ni190.505 23.241 79
Ce5Co190.504 64.857 138
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La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的相丰度和晶格参数统计结果

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R相结构相组成晶格参数相丰度/%
a/nmc/nm
LaCaCu5LaNi50.504 90.402 64
Ce2Ni7（LaMg）2Ni70.505 22.432 876
Pr5Co19（LaMg）5Ni190.505 83.237 36
Ce5Co190.505 54.855 814
NdCaCu5LaNi50.504 30.401 743
Ce2Ni7（LaMg）2Ni70.505 12.434 232
Pr5Co19（LaMg）5Ni190.504 63.246 94
Ce5Co190.504 54.851 421
SmCaCu5LaNi50.504 30.404 328
Ce2Ni7（LaMg）2Ni70.505 52.433 635
Pr5Co19（LaMg）5Ni190.505 23.241 79
Ce5Co190.504 64.857 138
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R相组成元素原子分数/%
AlMgNiLaNdSm
LaLaNi53.660.1479.4416.76——
（LaMg）2Ni71.154.1876.7417.93——
（LaMg）5Ni191.463.6378.4816.43——
NdLaNi52.840.7981.8013.441.13—
（LaMg）2Ni71.021.3076.5319.561.59—
（LaMg）5Ni191.030.1578.4418.342.01—
SmLaNi53.090.2180.4215.10—1.18
（LaMg）2Ni71.641.7976.0619.59—0.92
（LaMg）5Ni191.541.9678.9016.58—1.02
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La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的微区能谱分析

, figureFileSmall=null, figureFileBig=null, tableContent=
R相组成元素原子分数/%
AlMgNiLaNdSm
LaLaNi53.660.1479.4416.76——
（LaMg）2Ni71.154.1876.7417.93——
（LaMg）5Ni191.463.6378.4816.43——
NdLaNi52.840.7981.8013.441.13—
（LaMg）2Ni71.021.3076.5319.561.59—
（LaMg）5Ni191.030.1578.4418.342.01—
SmLaNi53.090.2180.4215.10—1.18
（LaMg）2Ni71.641.7976.0619.59—0.92
（LaMg）5Ni191.541.9678.9016.58—1.02
), ArticleFig(id=1241081046511449049, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081032800268435, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
R室温下24 h荷电保持率/%充放电循环100次后的容量保持率/%
La93.581.4
Nd97.585.8
Sm95.683.7
), ArticleFig(id=1241081046595335139, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081032800268435, language=CN, label=表3, caption=

La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的荷电保持率和容量保持率

, figureFileSmall=null, figureFileBig=null, tableContent=
R室温下24 h荷电保持率/%充放电循环100次后的容量保持率/%
La93.581.4
Nd97.585.8
Sm95.683.7
), ArticleFig(id=1241081046712775658, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081032800268435, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
R交换电流密度I0/（mA·g-1）电荷转移阻抗Rct/mΩ氢扩散系数D0/（10-10 cm2·s-1）
La299.55272.671.23
Nd435.66221.491.33
Sm365.63261.871.28
), ArticleFig(id=1241081048268862459, tenantId=1146029695717560320, journalId=1235980550691926019, articleId=1241081032800268435, language=CN, label=表4, caption=

La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的动力学参数

, figureFileSmall=null, figureFileBig=null, tableContent=
R交换电流密度I0/（mA·g-1）电荷转移阻抗Rct/mΩ氢扩散系数D0/（10-10 cm2·s-1）
La299.55272.671.23
Nd435.66221.491.33
Sm365.63261.871.28
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汽车电池用La-Mg-Ni基储氢合金的元素替代及电化学性能
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王飞 1 , 李丽君 2 , 梅琼珍 1 , 李振坤 3
矿冶工程杂志 | 电池材料专题 2024,44(4): 90-94
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矿冶工程杂志 | 电池材料专题 2024, 44(4): 90-94
汽车电池用La-Mg-Ni基储氢合金的元素替代及电化学性能
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王飞1 , 李丽君2, 梅琼珍1, 李振坤3
作者信息
  • 1.重庆科创职业学院，重庆 402160
  • 2.重庆理工大学，重庆 400054
  • 3.重庆大学，重庆 400044

    • 王飞（1979—），男，河北张家口人，硕士，副教授，主要研究方向为汽车电池。E-mail：

Element Substitution and Electrochemical Performance of La-Mg-Ni Based Hydrogen Storage Alloys for Automotive Batteries
Fei WANG1 , Lijun LI2, Qiongzhen MEI1, Zhenkun LI3
Affiliations
  • 1.Chongqing Creation Vocational College, Chongqing 402160, China
  • 2.Chongqing University of Technology, Chongqing 400054, China
  • 3.Chongqing University, Chongqing 400044, China
出版时间: 2024-08-01 doi: 10.3969/j.issn.0253-6099.2024.04.017
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摘要
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采用感应熔炼方法制备了La0.7R0.1Mg0.2Ni3.35Al0.15（R=La/Nd/Sm）储氢合金，研究了稀土元素Nd/Sm替代La对储氢合金相结构和电化学性能的影响。结果表明，采用Nd或Sm替代La时，储氢合金物相组成未发生改变，仍由LaNi5、（LaMg）2Ni7和（LaMg）5Ni19相组成，但储氢合金中LaNi5相和（LaMg）5Ni19相丰度会增加、（LaMg）2Ni7相丰度减小。R为La、Nd和Sm时储氢合金的最大放电比容量均在第2次充放电循环时获得，分别为377 mAh/g、382 mAh/g和376 mAh/g；采用Nd或Sm替代La，储氢合金高倍率放电性能、24 h荷电保持率和充放电循环100次时的容量保持率都不同程度地增加，且R为Nd时储氢合金的相应值最大。采用Nd或Sm替代La会使得储氢合金的交换电流密度、氢扩散系数增加，储氢合金电极的高倍率放电性能与交换电流密度和氢扩散系数变化趋势一致，表明储氢合金电极的高倍率放电性能由交换电流密度和氢扩散系数共同决定。

储氢合金  /  稀土掺杂  /  La  /  Nd  /  Sm  /  元素替代  /  相结构  /  电化学性能  /  汽车电池  /  La-Mg-Ni

A kind of hydrogen storage alloy of La0.7R0.1Mg0.2Ni3.35Al0.15 (R=La/Nd/Sm) was synthesized with induction melting method, and the effect of La substituted with rare earth element Nd/Sm on the phase structure, microstructure, and electrochemical performance of the hydrogen storage alloy was explored. The results show that the substitution of Nd or Sm for La doesn't change the phase composition of the hydrogen storage alloy, which is still composed of LaNi5, (LaMg)2Ni7, and (LaMg)5Ni19 phases, but leads to higher abundance of LaNi5 and (LaMg)5Ni19 phases, and lower abundance of (LaMg)2Ni7 phase in the hydrogen storage alloy. The hydrogen storage alloy, with La, Nd and Sm as R, deliver the maximum discharge capacities of 377 mAh/g, 382 mAh/g and 376 mAh/g, respectively, after the second charge-discharge cycle. With La substituted with Nd or Sm, the hydrogen storage alloy has its high-rate discharge capacity, the charge retention rate after 24 hours, and capacity retention rate after 100 cycles all improved to some extent, among which the hydrogen storage alloy with Nd as R is the best in all corresponding performance. Moreover, the substitution of La with Nd or Sm can make the hydrogen storage alloy with higher exchange current density and higher coefficient of hydrogen diffusion. Its high-rate discharge performance, exchange current density and hydrogen diffusion coefficient are all in in the same trend, indicating that high-rate discharge performance of the hydrogen storage depends on both exchange current density and hydrogen diffusion coefficient.

hydrogen storage alloy  /  substitution of rare earth element  /  La  /  Nd  /  Sm  /  elemental substitution  /  phase structure  /  electrochemical performance  /  automotive battery  /  La-Mg-Ni
王飞, 李丽君, 梅琼珍, 李振坤. 汽车电池用La-Mg-Ni基储氢合金的元素替代及电化学性能. 矿冶工程杂志, 2024 , 44 (4) : 90 -94 . DOI: 10.3969/j.issn.0253-6099.2024.04.017
Fei WANG, Lijun LI, Qiongzhen MEI, Zhenkun LI. Element Substitution and Electrochemical Performance of La-Mg-Ni Based Hydrogen Storage Alloys for Automotive Batteries[J]. Mining and Metallurgical Engineering, 2024 , 44 (4) : 90 -94 . DOI: 10.3969/j.issn.0253-6099.2024.04.017
正文
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La-Mg-Ni基储氢合金具有成本低、容量高、易活化等特性，在汽车电池用金属氢化物-镍（MH-Ni）电池负极材料领域受到广泛关注[1]。目前，La-Mg-Ni基储氢合金的研究热点主要集中在A/B侧元素替代[2-3]、制备工艺（球磨法[4]、快速凝固法[5-6]）、热处理（退火、冷却方式）等方面。此外，采用La、Ce、Pr等稀土元素替代A侧La元素来降低储氢合金生产成本以及改善储氢性能[7-9]的研究也有相关报道，并已证实添加稀土元素有助于改善储氢合金的电化学性能。而采用Nd、Sm元素部分替代La-Mg-Ni基储氢合金中Ni元素及其对相结构和电化学性能的影响规律方面的研究报道较少，具体作用机理也不清楚。本文选取稀土元素Nd、Sm为替代元素，对比分析了Nd/Sm部分替代La对La-Mg-Ni基无钴储氢合金相结构与电化学性能的影响，研究结果有助于开发出价格低廉、节能环保和电化学性能良好的汽车电池负极用La-Mg-Ni基储氢合金，并推动其在新能源汽车等领域的工业应用。
1 实验材料与方法
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1.1 实验原料
实验原料包括金属La、Nd、Sm、Mg、Ni和Al（纯度均高于99.2%），按照元素化学计量比在Nabertherm TOP16R/C440型真空感应炉中进行熔炼，并采用水冷铜模进行浇铸，得到La0.7R0.1Mg0.2Ni3.35Al0.15（R=La/Nd/Sm，下同）储氢合金铸锭，其中易烧损的Mg元素过量15%。在SAFtherm 1 200 ℃真空气氛箱式电阻炉中对储氢合金铸锭进行910 ℃、保温12 h的退火热处理，到温后随炉冷却至室温。采用ThermoFisher iCAP 6300型电感耦合等离子发射光谱仪测试退火态储氢合金的化学成分，直至退火态储氢合金的化学成分与设计成分相符。储氢合金电极和三电极测试系统制备所需原料[10]包括羟基镍粉（99.4%，0.074 mm）、烧结态Ni（OH）2/NiOOH、镍条、隔膜等。
1.2 储氢合金电极制备
将退火态储氢合金进行机械破碎、研磨并过400目（0.038 mm）筛得到储氢合金粉末，在RC-FA-1004E型电子天平上按羟基镍粉/储氢合金粉质量比1∶5称量并混合均匀，采用YKQ7-DY-30型电动粉末压片机在压力13 MPa、保压时间60 s条件下进行压片处理，制备得到直径1 cm、厚度1 mm的储氢合金电极片。
1.3 测试与表征
采用帕纳科panalytical多功能粉末X射线衍射仪分析储氢合金的物相组成；采用日立S-4800型扫描电子显微镜及附带能谱仪观察储氢合金的显微形貌和分析微区成分。在CBA IV PRO型电池测试仪上测试储氢合金电极的电化学性能[11]，测试前先采用点焊方法将储氢合金电极片与镍条进行焊接形成负极，并与烧结态Ni（OH）2/NiOOH和Hg/HgO（电解液为6 mol/L KOH溶液）组成三电极体系[12]，分别进行活化性能、高倍率放电性能、自放电性能、容量保持率、线性极化曲线、电化学阻抗谱和恒电位阶跃曲线测试。
2 结果与分析
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2.1 相结构
图1为La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的X射线衍射图谱，表1列出了对应储氢合金的相丰度和晶格参数统计结果。对比分析可知，当R为La时，储氢合金主要由CaCu5型结构的LaNi5相、Ce2Ni7型结构的（LaMg）2Ni7相、Pr5Co19型和Ce5Co19型结构的（LaMg）5Ni19相组成，对应的丰度分别为4%、76%、6%和14%；当R为Nd或Sm时，储氢合金物相组成并未发生改变，但对应相的晶格常数和相丰度都发生了改变，具体表现在：相较La时储氢合金中LaNi5相和（LaMg）5Ni19相丰度增加、（LaMg）2Ni7相丰度减小，晶胞体积有所减小，这主要是La的原子半径相对Nd/Sm更大，被Nd/Sm替代后储氢合金的晶胞体积减小，相应造成衍射峰角度向大角度偏移[13-14]。
2.2 显微形貌
La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的显微形貌和圆框所示区域的能谱分析结果分别见图2和表2。对比分析可知，当R为La、Nd和Sm时储氢合金的显微形貌中都出现了3种不同颜色的组织，分别对应图1中的3种相；结合图1与表2可知，图2中黑灰色区域为LaNi5相、灰白色区域为（LaMg）2Ni7相、白色区域为（LaMg）5Ni19相。此外，R为La、Nd和Sm时储氢合金中的3种相都含有Al、Mg、Ni和La元素，且CaCu5型结构的LaNi5相中Mg元素相对较少、Al元素相对较多；R为Nd时储氢合金中的3种相都含有Nd元素；R为Sm时储氢合金中的3种相都含有Sm元素。
2.3 电化学性能
图3为La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的室温活化曲线，充放电电流密度为72 mA/g。可见，在前10个循环周期内，随着充放电循环次数增加，储氢合金放电比容量先增加后减小，R为La、Nd和Sm时储氢合金的最大放电比容量都在第2次充放电循环时获得，分别为377 mAh/g、382 mAh/g和376 mAh/g。由此可见，La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金都具有良好的活化性能，这主要与储氢合金的自身相结构有关[15]，即都含有CaCu5型结构的LaNi5相、Ce2Ni7型结构的（LaMg）2Ni7相、Pr5Co19型和Ce5Co19型结构的（LaMg）5Ni19相，有助于抑制充放电过程中储氢合金的应变和晶格变形，且在吸放氢过程中可以为氢原子提供扩散通道[16]。整体而言，在相同充放电循环次数下，R为Nd的储氢合金的放电比容量最大，其次是R为La的储氢合金，再次是R为Sm的储氢合金。
图4为La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的高倍率放电性能。可见，放电电流密度从100 mA/g增至1 800 mA/g，R为La、Nd和Sm的储氢合金高倍率放电性能（HRD）都呈现逐渐减小的趋势，在相同放电电流密度下，R为Nd的储氢合金HRD最大，其次是R为Sm的储氢合金，再次是R为La的储氢合金。可见，采用Nd或Sm替代La，都有助于提升储氢合金的高倍率放电性能，且Nd替代La的效果要优于Sm，这主要是Nd或Sm替代的储氢合金中CaCu5型结构的LaNi5相丰度相对较高，而LaNi5相较其他相能更好地提高储氢合金倍率放电性能[17]。
La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金在室温下24 h荷电保持率（CR）和充放电循环100次时的容量保持率（S100）见表3。由表3可见，采用Nd或Sm替代La，储氢合金的CR和S100都不同程度地增加，且R为Nd的储氢合金CR和S100最大。La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的自放电性能和循环稳定性的变化主要与储氢合金中相组成及其含量有关[18]，由储氢合金中不同类型相与耐电化学腐蚀的对应关系可知，CaCu5型结构的LaNi5相抗腐蚀和粉化能力高于Pr5Co19型和Ce5Co19型结构的（LaMg）5Ni19相，且都高于Ce2Ni7型结构的（LaMg）2Ni7相[19]，Nd或Sm替代La后，储氢合金中LaNi5相和（LaMg）5Ni19相丰度增加，会不同程度提高储氢合金的自放电性能和循环稳定性[20]，且R为Nd的储氢合金中LaNi5相和（LaMg）5Ni19相丰度较高、（LaMg）2Ni7相丰度低，具有极佳的自放电性能和循环稳定性。
图5为La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金的线性极化曲线和电化学阻抗谱，测试温度为25 ℃，相应的动力学参数拟合结果见表4。从表4可知，R为La、Nd、Sm时，储氢合金的交换电流密度分别为299.55 mA/g、435.66 mA/g、365.63 mA/g，可见，采用Nd或Sm替代La会使储氢合金的交换电流密度增加，且R为Nd时交换电流密度更大；R为La、Nd、Sm时，储氢合金电荷转移阻抗分别为272.67 mΩ、221.49 mΩ和261.87 mΩ，即采用Nd或Sm替代La会使储氢合金的电荷转移电阻减小，且R为Nd时电荷转移电阻更小。整体而言，采用Nd或Sm替代La能改变储氢合金的相结构，从而改善储氢合金电极表面的电荷转移速率[21]，使储氢合金电极的电荷转移电阻减小、交换电流密度增大。
图6为La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金电极的时间-电流半对数曲线，测试温度为25 ℃，曲线拟合得到的氢扩散系数D0计算结果亦列于表4。在放电初期，储氢合金电极的电流会随着时间延长迅速降低；放电时间2 500 s时曲线拟合得到R为La、Nd、Sm时储氢合金电极的氢扩散系数D0分别为1.23×10-10、1.33×10-10、1.28×10-10 cm2/s，即采用Nd或Sm替代La会使得储氢合金的氢扩散系数D0增大，且R为Nd时氢扩散系数D0更大。
结合前述的储氢合金电极的交换电流密度的变化规律可知，La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金电极的高倍率放电性能、交换电流密度和氢扩散系数变化趋势一致，说明储氢合金电极的高倍率放电性能主要由交换电流密度和氢扩散系数决定，这主要与Nd或Sm替代La会使储氢合金电极的相结构发生变化有关[22]，即Nd或Sm替代La会使储氢合金中Ce2Ni7型结构的（LaMg）2Ni7相向CaCu5型结构的LaNi5相、Pr5Co19型和Ce5Co19型结构的（LaMg）5Ni19相转变，而LaNi5相和（LaMg）5Ni19相具有相对（LaMg）2Ni7相更好的倍率放电性能、自放电性能和循环稳定性等。
3 结论
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1）采用Nd或Sm替代La时，储氢合金物相组成未发生改变，仍然由CaCu5型结构的LaNi5相、Ce2Ni7型结构的（LaMg）2Ni7相、Pr5Co19型和Ce5Co19型结构的（LaMg）5Ni19相组成，且Nd或Sm替代La使储氢合金中LaNi5相和（LaMg）5Ni19相丰度增加、（LaMg）2Ni7相丰度减小，晶胞体积相对减小。
2）R为La、Nd和Sm时储氢合金的最大放电比容量都在第2次充放电循环时获得，分别为377 mAh/g、382 mAh/g和376 mAh/g。采用Nd或Sm替代La，都有助于提升储氢合金的高倍率放电性能，且Nd替代La的效果要优于Sm。
3）采用Nd或Sm替代La，储氢合金的24 h荷电保持率和充放电100次的容量保持率都不同程度地增加，且R为Nd时储氢合金的相应值更大。采用Nd或Sm替代La会使得储氢合金的交换电流密度增加、电荷转移电阻减小，且R为Nd时交换电流密度最大、电荷转移电阻最小。La0.7R0.1Mg0.2Ni3.35Al0.15储氢合金电极的高倍率放电性能、交换电流密度和氢扩散系统变化趋势一致。
基金
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  • 重庆市教委科技技术研究项目(KJQN202005404)
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2024年第44卷第4期
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doi: 10.3969/j.issn.0253-6099.2024.04.017
  • 接收时间：2024-03-04
  • 首发时间：2026-03-18
  • 出版时间：2024-08-01
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  • 收稿日期：2024-03-04
基金
重庆市教委科技技术研究项目(KJQN202005404)
作者信息
    1.重庆科创职业学院，重庆 402160
    2.重庆理工大学，重庆 400054
    3.重庆大学，重庆 400044
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https://castjournals.cast.org.cn/joweb/kygczz/CN/10.3969/j.issn.0253-6099.2024.04.017
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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