CN1093693C - 镧镨铈－镍系贮氢合金电极材料 - Google Patents

镧镨铈－镍系贮氢合金电极材料 Download PDF

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CN1093693C
CN1093693C CN99115178A CN99115178A CN1093693C CN 1093693 C CN1093693 C CN 1093693C CN 99115178 A CN99115178 A CN 99115178A CN 99115178 A CN99115178 A CN 99115178A CN 1093693 C CN1093693 C CN 1093693C
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hydrogen
electrode material
alloy electrode
lpc
laprce
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涂铭旌
陈云贵
唐定骧
李宁
阎康平
李全安
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Sichuan Baosheng new energy battery manufacturing Co. Ltd.
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Sichuan University
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Abstract

本发明提供一种镧镨铈-镍系贮氢合金电极材料，属AB5型，化学式为LPC(NiCoMnAl)5，式中，LPC是含钕原子比为0.0001～0.01的镧镨铈型混合稀土金属，LPC＝La1-x-yPrxCey，其中，x＝0.05～0.20，y＝0.03～0.15。本发明所用新型混合稀土金属几乎不含钕，制造成本低，充放电性能良好。

Description

镧镨铈-镍系贮氢合金电极材料
技术领域
本发明涉及一种贮氢合金电极材料，特别是涉及一种镧镨铈-镍系贮氢合金电极材料。
背景技术
稀土系贮氢合金是目前主要开发的贮氢合金材料，应用最为广泛，《金属学报》1996年6期题为“ML-Ni-Co-Al合金吸氢动力学”介绍了一种贮氢合金ML-Ni-Co-Al，其中A侧为富镧混合稀土金属，ML的组成(质量分数)为La＞40％，Ce＜10％，Pr＝5％～10％，Nd＝30％～40％。在该富镧混合稀土金属中钕含量高，而钕是轻稀土精矿中，稀土配分高、价值高且市埸好的元素之一，主要用于生产钕铁硼永磁材料等。另方面，随着氧化铈和氧化钕消费市埸不断扩大，提铈、提钕后剩下的大量镧镨铈混合稀土成为钕、铈生产中的副产物，大量堆积的副产物成为严重影响稀土产业平衡发展的制约因素。
发明内容
本发明目的在于解决稀土产业不平衡发展问题，提供一种以镧镨铈新型混合稀土金属为原料，制造成本低，其充放电性能良好的镧镨铈-镍系贮氢合金电极材料。
本发明镧镨铈-镍系贮氢合金电极材料为AB5型，化学式为LPG(NiCoMnAl)5，式中，LPC是含钕原子比为0.0001～0.01的镧镨铈型混合稀土金属，LPC＝La1-x-yPrxCey，其中，x＝0.05～0.20，y＝0.03～0.15。其中，镧镨铈型混合稀土金属的生产工艺是，采用传统的熔盐电解法，电解液是RECI3-KCI混合熔盐。原料RECI3是提钕、提铈、分除Sm、Eu、Gd后的含水镧镨铈混合氯化稀土，水分含量小于28％，粒度小于3mm，环境湿度小于45％，以石墨坩埚盛电解液兼作阳极，钨棒作阴极，电解液为RECI3∶KCI＝60～68∶32～40，控制电解液中REO浓度为21～25％，调整电解过程中电解电压为10～18V，电流1000～1100A，电解温度900～940℃，并随时清理阴极，在直流电埸的作用下，RE3+在阴极得电子还原成稀土金属，汇集于阴极下端的瓷皿中，电解后取出瓷皿，将电解产品铸锭、包装得成品镧镨铈新型混合稀土金属；B侧镍、钴、锰、铝采用纯度高于99.5％的金属元素为原料，为现有贮氢合金中B侧常用元素，其配比也采用目前常用的配比。
本发明镧镨铈-镍系贮氢合金电极材料的优点在于本发明采用镧镨铈型混合稀土用原料，几乎不含钕，不同于过去含钕的高镧混合稀土，这样在相当程度上缓解目前市埸和未来市埸钕铁硼永磁材料对金属钕的大量需求的矛盾，有助于混合稀土金属各元素的平衡利用，且该贮氢合金成本低于过去的贮氢合金，同时其充放电性能良好。
附图说明
图1：实施例1充放电试验
图2：实施例2充放电试验
具体实施方式
实施例1：本发明镧镨铈-镍系贮氢合金电极材料的化学组成是：
        LPG(Ni3.55Co0.75Mn0.4Al0.3)，式中，
         LPG＝La1-x-yPrxGey，
         其中，x＝0.09～0.13，y＝0.08～0.12。
制造方法是，按化学计量比配料共20公斤，材料装入真空感应电炉，抽真空，然后充氩气冲洗真空室，反复两次，最后充氩气开始保护熔炼，熔炼温度1400～1600℃，钢模浇铸得本发明贮氢合金。
充放电试验：合金锭初粉碎后，在真空球磨机中充氩气保护研磨，过200目筛，合金粉做成压Cu片电极作负极，正极为烧结氢氧化镍电极，参比电极为汞电极(Hg/HgO，6MKOH)，电解液为6MKOH。充放电制度为两种，一种为0.2C充7.5小时，0.2C放，截止电位-0.60V(相对于Hg/HgO)，温度20～25℃；另一种为0.4C充电3.5小时，0.4C放，截止电位-0.6V(相对于Hg/HgO)，温度20～25℃，测试结果如表1及图1。
测试结果表明，0.2C充放电的最大放电容量达331mAh/g，0.4C充放电的最大放电容量达316mAh/g，0.4C充放电300次后的放电容量达232mAh/g，与比较例相比较，本发明活化性能及高倍率放电性能与比较例相当，但0.2C和0.4C充放的最大放电容量更高，0.4C充放电循环300次的放电容量仍高于比较例放电容量。
实施例2：本发明镧镨铈-镍系贮氢合金电极材料的化学组成是：
        LPG(Ni3.75Co0.75Mn0.4Al0.3)，式中，
         LPC＝La1-x-yPrxCey，
         其中，x＝0.1～0.15，y＝0.05～0.08。
制造方法的充放电试验同实施例1，充放电试验测试结果如表1及图2。
测试结果表明，0.2C充放电的最大放电容量达334mAh/g，0.4C充放电的最大放电容量达309mAh/g，0.4C充放电300次后的放电容量达234mAh/g，与比较例相比较，本发明活化性能及高倍率放电性能与比较例相当，但0.2C和0.4C充放的最大放电容量更高，0.4C充放电循环300次的放电容量仍高于比较例放电容量。
表1：本发明贮氢合金的充放电性能测试结果
  序号 活化性能  0.2C充放最大放电容量mAh/g  0.4C充放最大放电容量mAh/g  0.4充放循环300次后的容量mAh/g  高倍率放电比率C1c/C0.2c
实施例1  2-4     331     316     232     81％
实施例2  2-4     334     309     234     80％
比较例  2-4     309     291     225     80％
比较例合金成份为：Mm(Ni3.55Co0.75Mn0.4Al0.3)，制造条件同实施例1。
图1：实施例1与比较例的充放电循环寿命试验结果。
图2：实施例2与比较例的充放电循环寿命试验结果。

Claims (1)

1、一种镧镨铈-镍系贮氢合金电极材料，属AB5型，其特征在于化学式为LPC(NiCoMnAl)5，式中，LPC是含钕原子比为0.0001～0.01的镧镨铈型混合稀土金属，LPG＝La1-x-yPrxCey，其中，x＝0.05～0.20，y＝0.03～0.15。
CN99115178A 1999-09-28 1999-09-28 镧镨铈－镍系贮氢合金电极材料 Expired - Lifetime CN1093693C (zh)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078827A (zh) * 1992-05-16 1993-11-24 上海工业大学 一种贮氢电极合金
CN1113963A (zh) * 1994-05-10 1995-12-27 中国科学院金属研究所 镍金属氢化物电池负极用储氢合金

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1078827A (zh) * 1992-05-16 1993-11-24 上海工业大学 一种贮氢电极合金
CN1113963A (zh) * 1994-05-10 1995-12-27 中国科学院金属研究所 镍金属氢化物电池负极用储氢合金

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