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Article(id=1199661549309756177, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1199661546335994621, articleNumber=1009-5438(2022)01-0039-05, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1637510400000, receivedDateStr=2021-11-22, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1763951201989, onlineDateStr=2025-11-24, pubDate=1645718400000, pubDateStr=2022-02-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763951201989, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763951201989, creator=13701087609, updateTime=1763951201989, updator=13701087609, issue=Issue{id=1199661546335994621, tenantId=1146029695717560320, journalId=1185652524569653253, year='2022', volume='48', issue='1', pageStart='1', pageEnd='98', issueExtLink='null', onlineDate='null', pubDate='1645718400000', pubDateStr='2022-02-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763951201279, creator='13701087609', updateTime=1763959528511, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1199696473341391309, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1199661546335994621, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1199696473341391310, tenantId=1146029695717560320, journalId=1185652524569653253, issueId=1199661546335994621, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=39, endPage=43, ext={EN=ArticleExt(id=1199661549691437850, articleId=1199661549309756177, tenantId=1146029695717560320, journalId=1185652524569653253, language=EN, title=Study on High Power Hydrogen Storage Alloy Powder, columnId=1187340472918880861, journalTitle=Science & Technology of Baotou Steel, columnName=Production Practice and Management, runingTitle=null, highlight=null, articleAbstract=

In this paper, a kind of high power hydrogen storage alloy powder is studied, its components such as main elements of rare earth and nickel as well as auxiliary elements of Co, Mn, Al and Fe are analyzed by inductively coupled plasma (ICP), its texture is analyzed by X-Ray Diffraction (XRD) test and the platform pressure curve is analyzed by reaction with the hydrogen. Moreover, the high power hydrogen storage electrode alloy is developed by carrying out the tests of particle size and specific surface area for hydrogen storage alloy powder as well as analyzing the electrochemical characteristics of alloy electrode. It is determined to meet the requirements of high power and current for Ni-MH battery by constant power test of battery. The charge-discharge performance with high current of Ni-MH battery is realized by optimizing the preparation technology of cathode.

, authors=null, authorsList=Wei-li Jiao, Fu-yi Huang, Xin Zhao, Chen Wang, Tao Hong, authorCompany=null, correspAuthors=null, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1199661552451289949, articleId=1199661549309756177, tenantId=1146029695717560320, journalId=1185652524569653253, language=CN, title=高功率储氢合金粉的研究, columnId=1185882039552193444, journalTitle=包钢科技, columnName=生产实践与管理, runingTitle=null, highlight=null, articleAbstract=

文章研究了一种高功率储氢合金粉,通过ICP测试对合金粉的主要元素稀土和镍、辅助元素钴、锰、铝、铁等成分进行分析,通过XRD测试进行合金粉组织结构分析,通过与氢气反应进行平台压曲线分析;同时进行储氢合金粉粒度和比表面积测试,以及合金电极的电化学特性分析,开发了高功率储氢电极合金。通过电池恒功率测试确定该高功率储氢电极合金可满足镍氢电池对高功率大电流的要求。通过优化负极电极制备工艺,实现镍氢电池的大电流充放电性能。

, authors=

焦伟利(1985-),女,内蒙古包头市人,工程师,现从事储氢材料工作。

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焦伟利(1985-),女,内蒙古包头市人,工程师,现从事储氢材料工作。

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焦伟利(1985-),女,内蒙古包头市人,工程师,现从事储氢材料工作。

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元素 试验设计要求 实际测量值
RE 30.0~34.0 32.2
Ni 58.0~61.0 59.7
Co 1.0~1.5 1.3
Mn 4.0~5.0 4.2
Al 1.0~1.5 1.2
Zr 0.3~0.5 0.36
Fe ≤0.1 0.003
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储氢合金元素含量标准要求(质量分数) %

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元素 试验设计要求 实际测量值
RE 30.0~34.0 32.2
Ni 58.0~61.0 59.7
Co 1.0~1.5 1.3
Mn 4.0~5.0 4.2
Al 1.0~1.5 1.2
Zr 0.3~0.5 0.36
Fe ≤0.1 0.003
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半峰宽 a/Å c/Å V/Å3
0.158 5.020 5 3.982 1 86.92
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XRD测试曲线数据

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半峰宽 a/Å c/Å V/Å3
0.158 5.020 5 3.982 1 86.92
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最大吸氢量Wmax
/%		 平台压力P
/MPa		 斜率F 滞后系数Hf
1.269 0.028 0.921 4 0.042 1
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PCT测试具体数据

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最大吸氢量Wmax
/%		 平台压力P
/MPa		 斜率F 滞后系数Hf
1.269 0.028 0.921 4 0.042 1
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粒度
型号		 筛分粒度分布(质量分数)/%
<0.106 mm <0.075 mm <0.053 mm <0.038 mm
150型 ≥90.0 60.0±5.0 33.0±5.0 <23.0
180型 ≥92.0 63.0±5.0 38.0±5.0 25.0±2.0
200型 100.0 >95.0 66.0±5.0 45.0±3.0
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储氢合金粉筛分粒度分布

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粒度
型号		 筛分粒度分布(质量分数)/%
<0.106 mm <0.075 mm <0.053 mm <0.038 mm
150型 ≥90.0 60.0±5.0 33.0±5.0 <23.0
180型 ≥92.0 63.0±5.0 38.0±5.0 25.0±2.0
200型 100.0 >95.0 66.0±5.0 45.0±3.0
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粒度型号 激光粒度分布/%
D10 D50 D90
150型 22.0±2.0 64.0±5.0 145.0±10.0
180型 18.0±2.0 55.0±4.0 125.0±15.0
200型 12.0±2.0 35.0±2.0 75.0±4.0
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储氢合金粉激光粒度分布

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粒度型号 激光粒度分布/%
D10 D50 D90
150型 22.0±2.0 64.0±5.0 145.0±10.0
180型 18.0±2.0 55.0±4.0 125.0±15.0
200型 12.0±2.0 35.0±2.0 75.0±4.0
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半电池 3C放电容量 5C放电容量 10C放电容量
常规合金粉半电池 252 146
高功率合金粉半电池 273 232 151
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半电池倍率放电对比表 mAh/g

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半电池 3C放电容量 5C放电容量 10C放电容量
常规合金粉半电池 252 146
高功率合金粉半电池 273 232 151
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高功率储氢合金粉的研究
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焦伟利 1 , 皇甫益 2 , 赵鑫 3 , 王晨 4 , 洪涛 4
包钢科技 | 生产实践与管理 2022,48(1): 39-43
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包钢科技 |生产实践与管理 2022 , 48 (1) : 39 -43
高功率储氢合金粉的研究
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焦伟利1, 皇甫益2, 赵鑫3, 王晨4, 洪涛4
作者信息
  • 1 内蒙古稀宝方元医疗科技有限责任公司,内蒙古 包头 014010
  • 2 内蒙古稀奥科镍氢动力电池有限公司,内蒙古 包头 014030
  • 3 内蒙古科技大学材料与冶金学院,内蒙古 包头 014010
  • 4 北方稀土检修服务分公司,内蒙古 包头 014010
Study on High Power Hydrogen Storage Alloy Powder
Wei-li Jiao1, Fu-yi Huang2, Xin Zhao3, Chen Wang4, Tao Hong4
Affiliations
  • 1 Re Treasure Foryou Medical Technology Co., Ltd., Baotou 014010, Inner Mongolia Autonomous Region, China
  • 2 Inner Mongolia Rare Earth Ovonic High-Power MH-Ni Battery Co., Ltd., Baotou 014030, Inner Mongolia Autonomous Region, China
  • 3 School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, Inner Mongolia Autonomous Region, China
  • 4 Maintenance Service Branch Co. of Northern Rare Earth High-tech Co., Ltd., Baotou 014010, Inner Mongolia Autonomous Region, China
出版时间: 2022-02-25
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摘要
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文章研究了一种高功率储氢合金粉,通过ICP测试对合金粉的主要元素稀土和镍、辅助元素钴、锰、铝、铁等成分进行分析,通过XRD测试进行合金粉组织结构分析,通过与氢气反应进行平台压曲线分析;同时进行储氢合金粉粒度和比表面积测试,以及合金电极的电化学特性分析,开发了高功率储氢电极合金。通过电池恒功率测试确定该高功率储氢电极合金可满足镍氢电池对高功率大电流的要求。通过优化负极电极制备工艺,实现镍氢电池的大电流充放电性能。

镍氢电池  /  储氢合金  /  动力  /  性能指标

In this paper, a kind of high power hydrogen storage alloy powder is studied, its components such as main elements of rare earth and nickel as well as auxiliary elements of Co, Mn, Al and Fe are analyzed by inductively coupled plasma (ICP), its texture is analyzed by X-Ray Diffraction (XRD) test and the platform pressure curve is analyzed by reaction with the hydrogen. Moreover, the high power hydrogen storage electrode alloy is developed by carrying out the tests of particle size and specific surface area for hydrogen storage alloy powder as well as analyzing the electrochemical characteristics of alloy electrode. It is determined to meet the requirements of high power and current for Ni-MH battery by constant power test of battery. The charge-discharge performance with high current of Ni-MH battery is realized by optimizing the preparation technology of cathode.

Ni-MH battery  /  hydrogen storage alloy  /  power  /  performance index
焦伟利, 皇甫益, 赵鑫, 王晨, 洪涛. 高功率储氢合金粉的研究. 包钢科技, 2022 , 48 (1) : 39 -43 .
Wei-li Jiao, Fu-yi Huang, Xin Zhao, Chen Wang, Tao Hong. Study on High Power Hydrogen Storage Alloy Powder[J]. Science & Technology of Baotou Steel, 2022 , 48 (1) : 39 -43 .
正文
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镍氢电池是继镍镉电池之后的新一代高能二次电池,由于它具有高容量、大功率、无污染等特点而备受人们青睐[1-2],特别是那些具有特殊功能的镍氢电池(如高功率镍氢电池用于混合动力汽车上),市场前景更是十分诱人。储氢合金作为镍氢电池负极主要原材料是20世纪60年代末发现的一类具有高存储氢密度的功能材料,从组成上大致可分为五类:稀土系AB5型(如LaNi5)、镁系(如Mg2Ni、MgNi、La2Mg17)、钛系AB型(如TiNi、TiFe)、锆、钛系Laves相AB2型(如ZrNi2)、钒系固溶体型(如(V0.9Ti0.1)1-xFex)。镍氢电池的性能与电极活性材料、电池整体设计及制作工艺等有关,其中储氢负极材料是关键的影响因素之一[3-4]。
1 储氢合金粉制作
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储氢合金的成分包括主要元素稀土和镍,及辅助元素钴、锰、铝、铁等。稀土元素包括镧(La)、铈(Ce)、镨(Pr)、钕(Nd),这4种元素在储氢合金中起到关键作用,稀土中La元素能够提高储氢合金粉的电化学容量,Ce和Pr(尤其是Ce)元素能够改善储氢合金粉的循环稳定性,可相对降低合金中Co的含量,但Ce含量过高使合金的平衡压升高,缩短电池的使用寿命。在稀土镍储氢合金中,LaNi5的氢化物平台压最低,CeNi5的最高,NdNi5和PrNi5介于两者之间,因此在混合稀土合金中调节La、Ce的相对含量可以在很大范围内调节合金的平台压,同时调整储氢材料的活化性能和滞后效应。
根据稀土、镍、钴等元素的特性以及方案要求,设计开发储氢合金粉。由于混合稀土金属中,镨钕含量比较少,为了降低成本,合理利用稀土元素,在储氢合金粉试验阶段设计成分时,储氢合金粉成分中去除镨钕稀土元素,并且降低钴的含量。按照设计好的成分进行熔炼、制粉,制作储氢合金样品。合金样品按照设计成分配料还需要考虑La、Mn等高蒸气压元素的烧损量,所用原料金属以及中间合金(如BFe、BNi)的纯度(质量分数)不小于99%。将合金机械破碎制得粒度小于35 μm的粉末。
1.1 ICP测试
通过ICP测试[5-6],储氢合金粉的成分符合镍氢电池的要求,具体见表1。
1.2 储氢合金粉的XRD测试分析
通过XRD测试分析进一步确定储氢合金粉的组织结构,见图1。
XRD曲线显示,储氢合金为CaCu5单相组织。CaCu5相的晶胞参数a、c和晶胞体积V的值见表2。
1.3 储氢合金粉平衡氢压
在室温下氢化物平衡压低有利于合金吸氢,改善吸放氢的可逆性。若平衡压高,产生的氢气将正极还原(放电反应),引起自放电现象。吸放氢的平台越长,吸氢量则越大,从而可获得高的电化学容量,因为电化学容量的大小与平台的宽度有很好的对应关系。
P-C-T(一定温度下,储氢合金的储氢量与其平衡压力关系的曲线)测试是将储氢合金在固态下直接与氢气发生反应并记录反应过程中的氢气压力,从而计算出吸放氢量的试验方法。它能够绘制出在测试温度下测量物质的压力-组成关系曲线。对储氢合金粉进行P-C-T测试,得到的P-C-T曲线平衡压适中而且吸放氢平台长,符合镍氢电池对高功率储氢合金粉的要求,见图2。
通过该测试曲线可以计算出最大吸氢量Wmax,平台压力P、滞后系数Hf及吸放氢平台的压力差以及斜率F,具体见表3。
1.4 储氢合金粉的粒度分布测试
储氢合金粉的粒度不但影响镍氢电池的充放电性能,而且影响电极的涂浆工艺。储氢合金粉粒度合适,负极材料就可以混合均匀并且负极材料可以均匀地涂覆在基材冲孔镀镍钢带上,不易脱落。通过对储氢合金粉进行筛分粒度和激光粒度的测试,分析该合金粉的粒度分布情况,具体见表4和表5。
通过对表4筛分粒度和表5激光粒度的分析,最符合粒度要求的是200型的合金粉。
1.5 比表面积测试
粒度小,反应面积大,反应速度快。选取常规合金对比测试,对高功率合金和常规合金的比表面积进行测试。通过激光粒度仪测试比表面积,高功率合金不同粒度下的比表面积大于常规合金的比表面积,而且比表面积随着合金粉粒径减小而增大(见图3)。
通过上述分析与测试,可得出结论:
(1)高功率储氢合金粉的吸放氢平台适中而且吸放氢平台长。
(2)200型高功率储氢合金粉粒度小,符合高功率要求。
(3)储氢合金粉粒度小,比表面积大,反应充分。
2 半电池制作及测试
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使用储氢合金制作成半电池,在常温25 ℃下,分别进行3C、5C和10C的放电性能测试(见图4),各测试5次。3C放电容量平均为273 mAh/g;5C放电容量平均为232 mAh/g;10 C放电容量平均为151 mAh/g。倍率放电性能比常规产品偏高,见表6。
由表6可知,高功率合金粉制作的半电池,倍率性能好,尤其是10倍率可以放电。
3 镍氢蓄电池的制作及测试
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为了验证储氢合金粉的倍率性能是否满足要求,在其他材料、工艺不变的情况下,使用该款储氢合金粉制作成镍氢电池进行测试。
恒功率测试是使用180 W的固定功率对电池进行10 s放电测试,通过截止电压判定性能。恒功率值是根据混合动力汽车实际工况确定,反应电池的大电流瞬间放电性能。通过测试,生产电池截止电压为0.852 V,试验电池(D01、D02)恒功率放电截止电压偏高,两只电池的截止电压都在0.9 V以上,满足混合动力汽车的功率要求,见图5。
通过电池测试看出,高功率合金粉制作的镍氢蓄电池,大电流性能好,恒功率180 W放电10 s,截至电压在0.9 V以上,满足混合动力汽车的功率要求。
4 结论
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(1)高功率储氢合金粉的吸放氢平台适中而且吸放氢平台长,合金粉粒度小,比表面积大,反应充分,符合高功率要求。
(2)高功率合金粉制作的半电池,倍率性能好,尤其是10倍率可以实现放电。
(3)高功率合金粉制作的镍氢蓄电池,大电流性能好,恒功率180 W放电10 s,截至电压在0.9 V以上,满足混合动力汽车的功率要求。

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参考文献 引证文献
排序方式：
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唐有根, 李文良. 镍氢电池[M]. 北京: 化学工业出版社, 2007.
[2]
徐绍萍, 李培良, 耿朝青. 镍氢电池用廉价稀土储氢合金负极材料的研制[J]. 稀土, 2004, 25(5):15-23.
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  • 接收时间：2021-11-22
  • 首发时间：2025-11-24
  • 出版时间：2022-02-25
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  • 收稿日期：2021-11-22
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    1 内蒙古稀宝方元医疗科技有限责任公司,内蒙古 包头 014010
    2 内蒙古稀奥科镍氢动力电池有限公司,内蒙古 包头 014030
    3 内蒙古科技大学材料与冶金学院,内蒙古 包头 014010
    4 北方稀土检修服务分公司,内蒙古 包头 014010
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2种不同金属材料的力学参数
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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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