[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

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

Info

Publication number
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
Authority
CN
China
Prior art keywords
alloy
hydrogen
storage alloy
temperature
lcp
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 - Lifetime
Application number
CNB2004100406492A
Other languages
English (en)
Other versions
CN1747202A (zh
Inventor
陈云贵
陶明大
涂铭旌
吴朝玲
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.)
SICHUAN BAOSHENG INDUSTRY CO LTD
Original Assignee
Sichuan University
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 Sichuan University filed Critical Sichuan University
Priority to CNB2004100406492A priority Critical patent/CN1326264C/zh
Publication of CN1747202A publication Critical patent/CN1747202A/zh
Application granted granted Critical
Publication of CN1326264C publication Critical patent/CN1326264C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2004100406492A CN1326264C (zh) 2004-09-09 2004-09-09 无钕稀土系低温贮氢合金电极材料

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2004100406492A CN1326264C (zh) 2004-09-09 2004-09-09 无钕稀土系低温贮氢合金电极材料

Publications (2)

Publication Number Publication Date
CN1747202A CN1747202A (zh) 2006-03-15
CN1326264C true CN1326264C (zh) 2007-07-11

Family

ID=36166616

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100406492A Expired - Lifetime CN1326264C (zh) 2004-09-09 2004-09-09 无钕稀土系低温贮氢合金电极材料

Country Status (1)

Country Link
CN (1) CN1326264C (zh)

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

Also Published As

Publication number Publication date
CN1747202A (zh) 2006-03-15

Similar Documents

Publication Publication Date Title
CN102956893A (zh) 一种低温镍氢电池及其制备方法
CN104532095A (zh) 一种钇-镍稀土系储氢合金
CN101626076A (zh) 一种高容量长寿命低成本稀土镁基储氢合金
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
CN111471895B (zh) 含钆和镍的储氢合金、负极、电池及制备方法
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
CN108511742B (zh) 一种单相a2b7型超晶格镨–镁–镍基合金电极材料及其制备方法
CN104152749A (zh) 添加锆、钛元素的a5b19型稀土-钇-镍系储氢合金
CN104513915A (zh) 添加锆、钛元素的ab3型稀土-钇-镍系储氢合金
CN108893656B (zh) La-Mg-Ni系A2B7型储氢合金及其制备方法
CN103456927B (zh) 含氧钒钛基贮氢电极合金及其制备方法
CN111118341B (zh) 稀土-钐-镍型储氢合金、负极、电池及制备方法
CN102888545B (zh) 一种镁基储氢合金的制备方法
CN111118342B (zh) A2B7型RE-Sm-Ni系储氢合金、负极、电池及制备方法
CN110492086B (zh) 一种储氢合金复合材料的制备方法
CN102054982A (zh) 一种低温镍氢电池用La-Mg-Ni型负极储氢材料
CN109390580B (zh) 一种钒基储氢合金及其制备方法和用途
Lv et al. An improvement of self-discharge properties of Ce2Ni7-type La0. 65Ce0. 1Mg0. 25Ni3Co0. 5 hydrogen storage alloy produced by the melt-spun processing
CN1326264C (zh) 无钕稀土系低温贮氢合金电极材料
CN111224092B (zh) 掺锆或钛的含钐储氢合金、负极、电池及制备方法
CN1173055C (zh) 镍-金属氢化物二次电池用新型稀土系贮氢电极合金
WEI et al. Phase structure and electrochemical properties of La1. 7+ xMg1. 3− x (NiCoMn) 9.3 (x= 0–0.4) hydrogen storage alloys
CN111118343B (zh) A2b7型含钆镍储氢合金、负极、电池及制备方法
CN114335510A (zh) 一种耐过充ab5型宽温区镍氢电池负极材料及其制备方法
CN101252184A (zh) 无钕稀土镁系低温贮氢电极合金

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
ASS Succession or assignment of patent right

Owner name: BAOSHENG INDUSTRY DEVELOPMENT CO., LTD., SICHUAN P

Free format text: FORMER OWNER: SICHUAN UNIVERSITY

Effective date: 20091023

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20091023

Address after: Floor 2, Wanfu building, No. three, 16 middle section, Renmin Road, Chengdu, Sichuan

Patentee after: Sichuan Baosheng Industry Co.,Ltd.

Address before: No. 23, south section of first ring road, Sichuan City, Chengdu Province

Patentee before: Sichuan University

EE01 Entry into force of recordation of patent licensing contract

Assignee: Sichuan Baosheng Industry Co.,Ltd.

Assignor: Sichuan University

Contract fulfillment period: 2007.2.6 to 2027.7.11

Contract record no.: 2009510000082

Denomination of invention: Non-neodymium rare-earth system electrode material with low-temperature hydrogen-storage alloy

Granted publication date: 20070711

License type: exclusive license

Record date: 20090924

LIC Patent licence contract for exploitation submitted for record

Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.2.6 TO 2027.7.11; CHANGE OF CONTRACT

Name of requester: BAOSHENG INDUSTRY DEVELOPMENT CO., LTD., SICHUAN P

Effective date: 20090924

EC01 Cancellation of recordation of patent licensing contract

Assignee: Sichuan Baosheng Industry Co.,Ltd.

Assignor: Sichuan University

Contract record no.: 2009510000082

Date of cancellation: 20110905

EE01 Entry into force of recordation of patent licensing contract

Assignee: SICHUAN BAOSHENG NEW ENERGY BATTERIES CO.,LTD.

Assignor: Sichuan Baosheng Industry Co.,Ltd.

Contract record no.: 2011510000248

Denomination of invention: Non-neodymium rare-earth system electrode material with low-temperature hydrogen-storage alloy

Granted publication date: 20070711

License type: Exclusive License

Open date: 20060315

Record date: 20110905

PP01 Preservation of patent right

Effective date of registration: 20120710

Granted publication date: 20070711

PD01 Discharge of preservation of patent

Date of cancellation: 20130710

Granted publication date: 20070711

PP01 Preservation of patent right

Effective date of registration: 20130710

Granted publication date: 20070711

RINS Preservation of patent right or utility model and its discharge
PD01 Discharge of preservation of patent
PD01 Discharge of preservation of patent

Date of cancellation: 20140110

Granted publication date: 20070711

PP01 Preservation of patent right
PP01 Preservation of patent right

Effective date of registration: 20140117

Granted publication date: 20070711

PD01 Discharge of preservation of patent

Date of cancellation: 20150117

Granted publication date: 20070711

RINS Preservation of patent right or utility model and its discharge
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20070711