CN1033654C - 一种贮氢电极合金 - Google Patents

一种贮氢电极合金 Download PDF

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Publication number
CN1033654C
CN1033654C CN92108425A CN92108425A CN1033654C CN 1033654 C CN1033654 C CN 1033654C CN 92108425 A CN92108425 A CN 92108425A CN 92108425 A CN92108425 A CN 92108425A CN 1033654 C CN1033654 C CN 1033654C
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alloy
hydrogen
lanthanum
cerium
rich
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CN1078827A (zh
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周自强
葛建生
张金龙
熊义辉
平信义
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Shanghai Polytechnic University
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Shanghai Polytechnic University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/383Hydrogen absorbing alloys
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/34Gastight accumulators
    • H01M10/342Gastight lead accumulators
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

本发明是一种氢镍电池用贮氢电极合金,它是以一定比例的富镧的稀土M1与一定比例的富铈的稀土Mm所组成的合金来取代LaNi5中的镧,用铜、钴、铝、锰等来取代部分镍所构成的合金。

Description

一种贮氢电极合金
本发明属于贮氢电极合金
常用的氢镍电池用贮氢材料主要有钛系和稀土系两大类,其中钛系贮氢合金由于其活化性能和动力学性能较差,特别是快速放电时其电压下降很快,因而影响了应用。日本开发了稀土系贮氢电极合金,对上述缺点有所克服,但其中钴含量较高,特别近年来钴价上涨幅度很大,使合金成本升高,因此人们希望能降低钴含量及合金价格。以含钴较少的日本专利MmNiaCobAlxMy系合金“水素吸藏合金电极”为例,(1989年6月27日,日本公开特许公报[A],平1-162741),其中Mm代表富铈的混合稀土元素(铈:45%,镧:30%,钕:5%,其他稀土元素20%),3.0≤a≤3.4,0.8≤b≤1.2,0.1≤x≤0.3,0.5≤y≤0.7。从中可见,钴的含量仍然较高,此外,该合金系还存在贮氢电极容量及循环寿命均偏低等缺点。
本发明的目的,在于克服上述贮氢电极合金的缺点,从而提供一种具有较低含钴量,并可进一步提高贮电容量和循环寿命的贮氢合金。
本发明通过以下配方得以实现。
Ml1-xMmxNi5-y(CoAlMn)yCuz合金系。
其中:Ml--富镧的混合稀土,其中镧:46~52%,铈:1~5%,钕:35~40%,镨:10~13%,钐:<2%,余下为其他稀土。
Mm-富铈的混合稀土,其中镧:23~27%,铈:46~52%,钕:16~20%,镨:5~10%,余下为其他稀土。
x=0.2~0.8
y=0.5~3.0,其中Co≤0.8
z=0.3~1.3
本发明是用一定比例的富镧混合稀土Ml与一定比例的富铈的混合稀土Mm所组成的合金来取代LaNi5中的镧,这可调节合金的吸放氢的平台压力,提高其贮氢贮电容量,同时用铜、钴、铝、锰来取代部分镍所构成的合金,特别是加入适量的铜,降低了钴的含量,可提高合金的循环寿命。
例如,Mm0.6Ml0.4Ni3.9(CoAlMn)1.1Cu0.5其贮电容量可达274mAh/g,循环寿命超过1000次。
当合金的其他成份相同时,用Ml1-xMmx替代部分Mm可明显提高其贮电容量,以Mm0.6Ml0.4Ni3.4(CoAlMn)1.6Cu0.5合金为例,其贮电容量比合金MmNi3.4(CoAlMn)1.6Cu0.5的贮电容量提高10%,由220mAh/g提高到240mAh/g。
表一为本发明一些贮氢合金的实例表一Ml1-xMmxNi5-y(CoAlMn)yCuz合金成分对贮氢性能的影响
    元素在分子式中的原子数   电极容量(mAh/g) 循环寿命
    Mm     Ml     Ni     (Co+Al+Mn)  Cu
    0.6    0.4    3.9    1.1         0.50.6    0.4    3.5    1.5         0.50.8    0.2    3.7    1.3         0.50.4    0.6    3.7    1.3         0.50.2    0.8    3.7    1.3         0.5     274258251256250  >1000次>1000次>1000次>1000次>1000次
用本合金系合金已制成近万支AA型及AAA型氢镍电池,其室温及-18℃用0.2C和1C放电性能及快速充电性能,皆符合镉-镍电池IEC国际标准,其循环寿命均大于1000次。
本发明的贮氢电极合金具有容量高,循环寿命长,成本低等优点,而且应用范围广,可用于制造各种不同用途和型号的民用及工业用氢镍电池的负极,以及用作加脱氢催化剂等,具有很大的经济效益。

Claims (1)

1.一种用于制造氢镍电池负极的贮氢合金,其特征在于是由富镧的稀土Ml与富铈的稀土Mm所组成的Ml1-xMmxNi5-y(CoAlMn)yCuz系合金。
其中:Ml-富镧的混合稀土,其中镧:46~52%,铈:1~5%,钕:35~40%,镨:10~13%,钐:(2%,余下为其他稀土。
Mm-富铈的混合稀土,其中镧:23~27%,铈:46~52%,钕:16~20%,镨:5~10%,余下为其他稀土。
x=0.2~0.8
y=0.5~3.0,其中Co≤0.8
z=0.3~1.3
CN92108425A 1992-05-16 1992-05-16 一种贮氢电极合金 Expired - Fee Related CN1033654C (zh)

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CN92108425A CN1033654C (zh) 1992-05-16 1992-05-16 一种贮氢电极合金

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Application Number Priority Date Filing Date Title
CN92108425A CN1033654C (zh) 1992-05-16 1992-05-16 一种贮氢电极合金

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CN1078827A CN1078827A (zh) 1993-11-24
CN1033654C true CN1033654C (zh) 1996-12-25

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056017C (zh) * 1994-08-10 2000-08-30 北京有色金属研究总院 碱性蓄电池负极用的储氢合金材料及其制法
CN1044174C (zh) * 1994-10-20 1999-07-14 浙江大学 一种贮氢合金电极材料
CN1056018C (zh) * 1994-10-25 2000-08-30 北京有色金属研究总院 碱性蓄电池负极用的储氢合金材料及其制法
CN1050450C (zh) * 1995-12-22 2000-03-15 威海文隆电池有限公司 氢电极用贮氢合金材料
US6602639B1 (en) * 1997-12-26 2003-08-05 Toyota Jidosha Kabushiki Kaisha Process for producing hydrogen storage alloy and process for producing hydrogen storage alloy electrode
CN1093693C (zh) * 1999-09-28 2002-10-30 四川大学 镧镨铈-镍系贮氢合金电极材料
CN102899681A (zh) * 2012-10-26 2013-01-30 华侨大学 多孔镍复合电极、电镀液及该多孔镍复合电极的制备方法

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