CN1329542C - 一种稀土镁基贮氢合金 - Google Patents

一种稀土镁基贮氢合金 Download PDF

Info

Publication number
CN1329542C
CN1329542C CNB200510034916XA CN200510034916A CN1329542C CN 1329542 C CN1329542 C CN 1329542C CN B200510034916X A CNB200510034916X A CN B200510034916XA CN 200510034916 A CN200510034916 A CN 200510034916A CN 1329542 C CN1329542 C CN 1329542C
Authority
CN
China
Prior art keywords
alloy
rare earth
storage alloy
magnesium base
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB200510034916XA
Other languages
English (en)
Other versions
CN1718814A (zh
Inventor
肖方明
唐仁衡
卢其云
彭能
王英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Institute of Rare Metals
Original Assignee
Guangzhou Research Institute of Non Ferrous Metals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Research Institute of Non Ferrous Metals filed Critical Guangzhou Research Institute of Non Ferrous Metals
Priority to CNB200510034916XA priority Critical patent/CN1329542C/zh
Publication of CN1718814A publication Critical patent/CN1718814A/zh
Application granted granted Critical
Publication of CN1329542C publication Critical patent/CN1329542C/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

本发明涉及一种稀土镁基贮氢合金。其特征是该合金的通式为LaaCebPrcNddMgeNifCogMnhAli,式中a+b+c+d+e∶f+g+h+i=1∶2.6~3.7,其中:a+b+c+d+e=1,0.1≤a≤0.3,0.01≤b≤0.1,0.2≤c≤0.45,0.01≤d≤0.3,0.05≤e≤0.3;2.4≤f≤3.2,0.05≤g≤0.2,0.01≤h≤0.15,0.05≤i≤0.25。本发明提供的贮氢合金的Pr含量占稀土合金总量的40~50%,合金的循环性能得到明显提高,循环寿命可达到300次以上。该合金还具有容量高、成本低等特点,适合高容量电池使用。

Description

一种稀土镁基贮氢合金
技术领域
本发明涉及一种镍-金属氢化物电池负极材料,特别涉及一种贮氢合金。
背景技术
近年来,镍氢电池在高容量、高功率方向得到迅速发展。作为镍氢电池的关键负极材料,要求具有高容量、循环性能好、大电流放电性能好、成本低等特点。
而目前使用的稀土基AB5型贮氢合金比容量提高空间不大,约为280-320mAh/g左右。近年来,一种新型AB3型稀土镁基贮氢合金受到广泛关注,该合金吸氢量较大、放电容量高、活化快、大电流放电性能好,其可逆吸氢量可达到1.8~1.87%,理论放电比容量可达到400mAh/g,大大高于AB5型合金粉。目前,AB3型结构贮氢合金研究存在的主要问题是循环寿命差。为提高贮氢合金的循环性能,主要用稀土合金代替金属La、用Co、Fe、Mn、Al、B等元素代替金属Ni以及调整其A、B侧化学计量比。
文献(1)(《电池》,2004,5:316-318)制备了一种La2Mg(Ni0.85Co0.15)9B0.1稀土镁基合金贮氢合金,其最大放电比容量为390.02mAh/g,但循环性能没有明显提高,100次比容量衰减为38.5%。
为提高稀土镁基贮氢合金循环性能,中国专利01131896.1采用了一种富铈Mm1-YMY(NiCoN)X稀土镁基合金贮氢合金,其中0.01≤Y≤0.8,2.0≤X≤4.0,其循环性能明显提高。其中稀土元素总含量不低于90wt%,Ce含量不低于70wt%,La含量不高于30wt%,放电比容量较低。
发明内容
本发明的目的是提供一种具有PuNi3型结构,合金粉活化快、容量高、大电流放电性能好、Co含量低等特点的高镨稀土镁基贮氢合金。
本发明的目的是这样实现的:
该稀土镁基合金的通式为LaaCebPrcNddMgeNifCogMnhAli,式中a+b+c+d+e∶f+g+h+i=1∶2.6~3.7,其中:a+b+c+d+e=1,0.1≤a≤0.3,0.01≤b≤0.1,0.2≤c≤0.45,0.01≤d≤0.3,0.05≤e≤0.3;2.4≤f≤3.2,0.05≤g≤0.2,0.01≤h≤0.15,0.05≤i≤0.25。按通式原子比例配料,在氩气保护条件下,中频感应炉熔炼,得到合金锭,合金锭在850~1050℃条件下,保温热处理2~24h.,冷却至室温,粉碎至<100~300目。
取制得的合金粉0.2g与羰基镍粉以重量比1∶3均匀混合,在20Mpa的压力下制得直径为15mm的电极片。合金粉的电化学性能测试为双电极体系,对电极为烧结镍电极,容量为1200mAh,电解液用6mol/LKOH+0.5molLiOH溶液,测试温度:25~28℃。
本发明提供的贮氢合金的Pr含量占稀土合金总量的40~50%,合金的循环性能得到明显提高,循环寿命可达到300次以上。该合金还具有容量高、成本低等特点,适合高容量电池使用。
图1是实施例4的贮氢合金的X-射线衍射图;
图2是实施例4的贮氢合金的放电曲线;
表1是贮氢合金的性能对比。
具体实施方式
实施例1
按通式为La0.2Ce0.1Pr0.33Nd0.19Mg0.18Ni2.48Co0.10Mn0.05Al0.10的各金属原子比称取金属原料5kg,在氩气保护条件下,中频感应炉熔炼,得到合金锭,合金锭在900℃条件下,保温热处理2h.,然后冷却至室温,机械粉碎至<200目。
实施例2
通式为La0.15Ce0.05Pr0.4Nd0.15Mg0.25Ni2.60Co0.18Mn0.08Al0.14。其他同实施例1。
实施例3
通式为La0.25Ce0.05Pr0.4Nd0.12Mg0.18Ni2.95Co0.18Mn0.08Al0.19。其他同实施例1。
实施例4
通式为La0.2Ce0.1Pr0.33Nd0.19Mg0.18Ni3.05Co0.2Mn0.09Al0.16。其他同实施例1。
该合金粉的X-射线衍射谱图如图1所示,放电曲线如图2所示。
取制得的合金粉0.2g与羰基镍粉,以重量比1∶3均匀混合,在20MPa的压力下,制得直径为15mm的电极片。在三电极体系中,以烧结镍电极(容量为1200mAh)为对电极,电解液用6mol/LKOH+0.5molLiOH溶液,测试合金粉的电化学性能。以72mA/g电流充电360分钟,静置5分钟,以72mA/g电流放电至1.0V,测试合金粉的放电比容量。以720mA/g电流充电36分钟,静置5分钟,以720mA/g电流放电至1.0V,测试合金粉的循环性能。
从图1可看出,合金为PuNi3晶型结构。
从表1可看出,本发明的高镨稀土镁基贮氢合金循环寿命均达到300次以上,放电比容量可达到371~393mAh/g。与文献(1)纯La稀土镁基贮氢合金相比,其循环寿命得到明显的改善。与中国专利01131896.1富铈稀土镁基贮氢合金相比,本发明的贮氢合金放电比容量明显较高。
表1贮氢合金的性能对比
样品   比容量(mAh/g)   300循环容量衰减(S300/%)
实施例1   371   19
实施例2   393   16
实施例3   387   14
实施例4   384   13
文献(1)稀土镁基合金 390 S100=38.5
01131896.1稀土镁基合金 366 15

Claims (1)

1.一种稀土镁基贮氢合金,其特征是该合金的通式为LaaCebPrcNddMgeNifCogMnhAli,式中a+b+c+d+e∶f+g+h+i=1∶2.6~3.7,其中:a+b+c+d+e=1,0.1≤a≤0.3,0.01≤b≤0.1,0.2≤c≤0.45,0.01≤d≤0.3,0.05≤e≤0.3;2.4≤f≤3.2,0.05≤g≤0.2,0.01≤h≤0.15,0.05≤i≤0.25。
CNB200510034916XA 2005-05-31 2005-05-31 一种稀土镁基贮氢合金 Expired - Fee Related CN1329542C (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB200510034916XA CN1329542C (zh) 2005-05-31 2005-05-31 一种稀土镁基贮氢合金

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB200510034916XA CN1329542C (zh) 2005-05-31 2005-05-31 一种稀土镁基贮氢合金

Publications (2)

Publication Number Publication Date
CN1718814A CN1718814A (zh) 2006-01-11
CN1329542C true CN1329542C (zh) 2007-08-01

Family

ID=35930762

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200510034916XA Expired - Fee Related CN1329542C (zh) 2005-05-31 2005-05-31 一种稀土镁基贮氢合金

Country Status (1)

Country Link
CN (1) CN1329542C (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103101880B (zh) * 2013-01-29 2014-11-12 广州有色金属研究院 一种硼氢化锂/稀土镁基合金复合储氢材料及其制备方法
CN109830676B (zh) * 2019-01-21 2020-10-13 江苏集萃安泰创明先进能源材料研究院有限公司 二次可充电镍氢电池用La-Mg-Ni型负极储氢材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1406396A (zh) * 1999-12-27 2003-03-26 株式会社东芝 贮氢合金、二次电池、混合型汽车及电动汽车
CN1445375A (zh) * 2003-03-24 2003-10-01 浙江大学 新型贮氢合金及其制备和淬火处理方法
CN1445376A (zh) * 2003-03-24 2003-10-01 浙江大学 镍-金属氢化物二次电池用新型贮氢合金及其制备和退火处理方法
JP2004296190A (ja) * 2003-03-26 2004-10-21 Sanyo Electric Co Ltd ニッケル−水素蓄電池
JP2005023341A (ja) * 2003-06-30 2005-01-27 Yuasa Corp 水素吸蔵合金及びその製造方法、並びに、これを用いたニッケル水素蓄電池
CN1610151A (zh) * 2004-09-17 2005-04-27 西安交通大学 一种低钴稀土系镍氢电极合金

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1406396A (zh) * 1999-12-27 2003-03-26 株式会社东芝 贮氢合金、二次电池、混合型汽车及电动汽车
CN1445375A (zh) * 2003-03-24 2003-10-01 浙江大学 新型贮氢合金及其制备和淬火处理方法
CN1445376A (zh) * 2003-03-24 2003-10-01 浙江大学 镍-金属氢化物二次电池用新型贮氢合金及其制备和退火处理方法
JP2004296190A (ja) * 2003-03-26 2004-10-21 Sanyo Electric Co Ltd ニッケル−水素蓄電池
JP2005023341A (ja) * 2003-06-30 2005-01-27 Yuasa Corp 水素吸蔵合金及びその製造方法、並びに、これを用いたニッケル水素蓄電池
CN1610151A (zh) * 2004-09-17 2005-04-27 西安交通大学 一种低钴稀土系镍氢电极合金

Also Published As

Publication number Publication date
CN1718814A (zh) 2006-01-11

Similar Documents

Publication Publication Date Title
Miao et al. Influences of Co substitution and annealing treatment on the structure and electrochemical properties of hydrogen storage alloys La0. 7Mg0. 3Ni2. 45-xCo0. 75+ xMn0. 1Al0. 2 (x= 0.00, 0.15, 0.30)
Zhang et al. La–Mg–Ni ternary hydrogen storage alloys with Ce2Ni7-type and Gd2Co7-type structure as negative electrodes for Ni/Mh batteries
CN104152749B (zh) 添加锆、钛元素的a5b19型稀土‑钇‑镍系储氢合金
CN104513925B (zh) 一种钇‑镍稀土系储氢合金及含该储氢合金的二次电池
CN104532095A (zh) 一种钇-镍稀土系储氢合金
CN104513915B (zh) 添加锆、钛元素的ab3型稀土‑钇‑镍系储氢合金
CN102104146B (zh) 一种镍氢电池用无钴ab3.5型储氢合金负极材料及其制备方法
Zhang et al. Study on solid solubility of Mg in Pr3− xMgxNi9 and electrochemical properties of PuNi3-type single-phase RE–Mg–Ni (RE= La, Pr, Nd) hydrogen storage alloys
CN104532062A (zh) 一种钇-镍稀土系储氢合金
CN106119652A (zh) 镍氢电池用La‑Mg‑Ni系储氢合金及其制备方法
CN104513916A (zh) 添加锆、钛元素的a2b7型稀土-钇-镍系储氢合金
CN101417786B (zh) La15Fe77B8型储氢合金及其用途
Tang et al. Study on the microstructure and the electrochemical properties of Ml0. 7Mg0. 2Ni2. 8Co0. 6 hydrogen storage alloy
CN1329542C (zh) 一种稀土镁基贮氢合金
CN101626078B (zh) 镍氢电池用La-Mg-Ni型负极储氢材料
Wang et al. Electrochemical hydrogen storage properties of the ball-milled PrMg12− xNix+ 150 wt% Ni (x= 1 and 2) composites
CN103456927B (zh) 含氧钒钛基贮氢电极合金及其制备方法
CN100467640C (zh) Ab3.5型负极储氢材料的制备方法及其制得的材料和用途
Zhang et al. Structures and electrochemical hydrogen storage behaviours of La0. 75− xPrxMg0. 25Ni3. 2Co0. 2Al0. 1 (x= 0–0.4) alloys prepared by melt spinning
Liu et al. Electrochemical properties of Ti-based Quasicrystal and ZrV2 Laves phase alloy composite materials as negative electrode for Ni–MH secondly batteries
Guo et al. The effect of Ni content on the phase structures and electrochemical properties of V2. 1TiNix (x= 0.1–0.9) hydrogen storage alloys
Fan et al. Microstructures and electrochemical hydrogen storage performances of La0. 75Ce0. 25Ni3. 80Mn0. 90Cu0. 30 (V0. 81Fe0. 19) x (x= 0–0.20) alloys
CN102054982A (zh) 一种低温镍氢电池用La-Mg-Ni型负极储氢材料
WO2002043170A2 (en) Metal hydride battery material with high storage capacity
Feng et al. Effect of Al and Ce substitutions of the electrochemical properties of amorphous MgNi-based alloy electrodes

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20060111

Assignee: Jinyuan Rare Earth Co., Ltd.Guangxi Nonferrous Metals Group

Assignor: Guangzhou Research Institute of Non-ferrous Metals

Contract record no.: 2009450000123

Denomination of invention: Rare earth magnesium base hydrogen storage alloy

Granted publication date: 20070801

License type: Exclusive License

Record date: 20091216

TR01 Transfer of patent right

Effective date of registration: 20180104

Address after: 510651 Changxin Road, Guangzhou, Guangdong, No. 363, No.

Patentee after: GUANGDONG INSTITUTE OF RARE METALS

Address before: Wushan 510651 Guangdong city of Guangzhou Province

Patentee before: Guangzhou Research Institute of Non-ferrous Metals

TR01 Transfer of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20070801

Termination date: 20190531

CF01 Termination of patent right due to non-payment of annual fee