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CN1326264C - 无钕稀土系低温贮氢合金电极材料 - Google Patents

无钕稀土系低温贮氢合金电极材料 Download PDF

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CN1326264C
CN1326264C CNB2004100406492A CN200410040649A CN1326264C CN 1326264 C CN1326264 C CN 1326264C CN B2004100406492 A CNB2004100406492 A CN B2004100406492A CN 200410040649 A CN200410040649 A CN 200410040649A CN 1326264 C CN1326264 C CN 1326264C
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low
temperature
alloy
hydrogen storage
storage alloy
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CN1747202A (zh
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陈云贵
陶明大
涂铭旌
吴朝玲
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SICHUAN BAOSHENG INDUSTRY CO LTD
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Sichuan University
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    • Y—GENERAL 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

本发明提供了一种无钕稀土系低温贮氢合金电极材料，该合金解决了普通贮氢合金在-20℃～-50℃下放电性能很差的问题，且该合金还具有较好的常温放电性能。该合金属AB5型，化学式为LCP(NiCoMnAl)5，式中LCP为镧铈镨混合稀土金属，LCP＝La1-x-yCexPry，其中，x＝0.55～0.85，y＝0.02～0.15。该合金用于制造低温镍氢电池或宽温区镍氢电池。

Description

无钕稀土系低温贮氢合金电极材料
技术领域
本发明涉及一种稀土系贮氢合金电极材料，特别是涉及一种适用于25℃～-50℃条件下使用的无钕稀土系贮氢合金电极材料，该合金用于制造低温镍氢电池或宽温区镍氢电池。
背景技术
镍氢电池因其比能量高、不污染环境、无记忆效应、循环寿命长以及具有良好的耐过充过放电特性，得到了广泛的应用。但在一些特殊的条件下，如野外军用电台、飞机和坦克等军事装置及非常寒冷的地区，镍氢电池的应用受到很大的限制。其原因是普通镍氢电池的低温性能较差，一般只能在-20℃的条件下放电，当温度低于-20℃时，电池的放电性能急剧下降，尤其是高倍率放电性能，而军事装置和寒冷地区要求电池能在-40℃甚至更低的环境下放电。研究表明，决定镍氢电池低温性能的主要因素是负极的贮氢合金，因此要解决镍氢电池低温放电问题，必须要解决贮氢合金的低温放电问题。中国专利1309433公开了一种AB3型非化学计量比低温贮氢合金电极材料，其适用温度为-25℃，放电电流为45mAh/g。
发明内容
本发明目的在于解决贮氢合金的低温放电性能差的问题，提供一种在25℃～-50℃条件下放电性能良好的贮氢合金。
本发明无钕稀土系低温贮氢合金电极材料属AB5型，化学式为LCP(NiCoMnAl)5，式中LCP为镧铈镨混合稀土金属，LCP＝La1-x-yCexPry，其中，x＝0.55～0.85，y＝0.02～0.15。A侧为无钕富铈混合稀土金属。无钕富铈混合稀土金属的生产工艺采用传统的熔盐电解法，同中国专利99115178.X。不同的是，采用熔盐电解法得到的无钕富铈混合稀土金属还需要进行重熔净化处理。重熔的方法是，将电解所得无钕富铈混合稀土金属在轻质熔盐氯化钠和氟化锂覆盖下进行熔炼，使夹杂和氧化物等进入熔盐，得本发明用净化后的无钕富铈混合稀土金属；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。
与普通的贮氢合金相比，本发明无钕稀土系低温贮氢合金的优点是可以在25℃～-50℃条件下以0.2C和0.4C放电。
附图说明
图1：无钕稀土系低温贮氢合金25℃下0.2C(60mAh/g)放电曲线。
图2：无钕稀土系低温贮氢合金25℃下1C(300mAh/g)放电曲线。
图3：无钕稀土系低温贮氢合金-40℃下0.2C(60mAh/g)放电曲线。
图4：无钕稀土系低温贮氢合金-40℃下0.4C(120mAh/g)放电曲线。
具体实施方式
实施例：本发明无钕稀土系低温贮氢合金的化学组成为：
LCP(NiCoMnAl)5，式中，LCP＝La1-x-yCexPry，其中，x＝0.58～0.62，y＝0.06～0.08。
制造方法是，首先将电解所得无钕富铈混合稀土金属在轻质熔盐氯化钠和氟化锂覆盖下进行熔炼，让夹杂和氧化物等进入熔盐，使富铈混合稀土金属得到净化。按贮氢合金的化学计量比配料共20公斤，将材料装入真空感应炉，抽真空，然后充氩气洗真空室，反复两次，最后充入氩气开始熔炼，熔炼温度为1400～1600℃，铜模浇注得本发明无钕稀土系低温贮氢电极合金锭。
充放电试验：将上述贮氢合金粗破碎后，在真空球磨机中充氩气保护研磨，过200目筛得实验所用的贮氢合金粉。将合金粉与镍粉按1∶3的比例混合均匀，在3.5MPa压力下冷压成10mm的薄片作为研究电极，辅助电极为烧结式氢氧化亚镍电极，参比电极为汞/氧化汞(Hg/HgO)电极，电解液为8M/L KOH溶液，隔膜为聚丙烯毡。电化学性能测试设备为国产DC-5型电池测试仪。活化制度是先用0.2C活化10次，再用1C活化10次，环境温度为25℃。0.2C活化时，充放电电流均为60mA·g-1，充电7h，放电截止电位均为-0.6V(vs.Hg/IIgO，8M KOH)；1C活化时，充放电电流均为300mA·g-1，充电时间为1.2h，放电截止电位均为-0.6V(vs.Hg/HgO，8M KOH)。
进行低温性能测试时，将活化好的电池用1C充电1.2小时，然后在低温箱内放置5小时后进行放电。放电制度为0.4C和0.2C，环境温度为-40℃。0.4C放电，放电电流为120mA·g-1，放电截止电位均为0V(vs.Hg/HgO，8M KOH)；0.2C放电，放电电流约为60mA·g-1，放电截止电位均为-0.6V(vs.Hg/HgO，8M KOH)。
从图1和图2可以看出，本发明合金在25℃下0.2C放电容量超过300mAh/g，1C放电容量超过270mAh/g，与普通贮氢合金放电容量相当。
从图3可以看出，在-40℃和0.2C放电条件下，本发明合金容量超过190mAh/g，普通合金容量为17mAh/g。从图4可以看出，在-40℃和0.4C放电条件下，本发明合金容量超过130mAh/g，普通合金容量为6mAh/g。

Claims (1)

1.一种无钕稀土系低温贮氢合金电极材料，属AB5型，其特征在于化学式为LCP(NiCoMnAl)5，式中LCP为镧铈镨混合稀土金属，LCP＝La1-x-yCexPry，其中，x＝0.55～0.85，y＝0.02～0.15。
CNB2004100406492A 2004-09-09 2004-09-09 无钕稀土系低温贮氢合金电极材料 Expired - Lifetime CN1326264C (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753386A (en) * 1995-09-29 1998-05-19 Kabushiki Kaisha Toshiba Hydrogen-absorbing alloy for battery and secondary nickel-metal hydride battery
CN1251472A (zh) * 1999-09-28 2000-04-26 四川大学 低Co镧镨铈－镍系贮氢合金电极材料
CN1424782A (zh) * 2002-12-27 2003-06-18 四川大学 镍氢动力电池用无钕稀土贮氢合金

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5753386A (en) * 1995-09-29 1998-05-19 Kabushiki Kaisha Toshiba Hydrogen-absorbing alloy for battery and secondary nickel-metal hydride battery
CN1251472A (zh) * 1999-09-28 2000-04-26 四川大学 低Co镧镨铈－镍系贮氢合金电极材料
CN1424782A (zh) * 2002-12-27 2003-06-18 四川大学 镍氢动力电池用无钕稀土贮氢合金

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