CN1044174C - 一种贮氢合金电极材料 - Google Patents
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- 239000000956 alloy Substances 0.000 title claims abstract description 59
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 58
- 239000007772 electrode material Substances 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 abstract description 24
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001122 Mischmetal Inorganic materials 0.000 abstract description 13
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 9
- -1 hydride-nickel Chemical compound 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000003860 storage Methods 0.000 description 22
- 229910052779 Neodymium Inorganic materials 0.000 description 15
- 229910052761 rare earth metal Inorganic materials 0.000 description 14
- 150000002910 rare earth metals Chemical class 0.000 description 13
- 229910052777 Praseodymium Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000000470 constituent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- 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
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Abstract
一种贮氢合金电极材料,其特征是它的化学式为:
M1αMm1-αNi5-x-y-zCoxMnyTiz,
式中0<α<1,x=0.5~1.0,y=0.3~0.6,z=0.01~0.1,优先选用的化学式为M10.85Mm0.15Ni3.8Co0.75Mn0.4Ti0.05,其中M1是市售的富镧混合稀土金属,Mm是富铈混合稀土金属。应用本发明材料制成的氢化物-镍电池,其活化性能、起始容量、高倍放电性能、循环寿命等项技术性能指标皆优于现有技术。
Description
本发明涉及选择一种作为碱性蓄电池电极活性物质用的合金,特别涉及一种含有混合稀土金属的贮氢合金电极材料。
目前,以含有稀土金属的贮氢合金作为负极活性物质的氢化物-镍电池,由于具有易活化、较高的电化学容量、抗腐蚀、较长的循环寿命、良好的电极反应可逆性、价格低廉、无环境污染等诸多优点,格外引人注目,尤其是AB5型稀土-镍系贮氢合金成为小型密封氢化物-镍电池工业化生产中首选的贮氢合金电极材料。
关于AB5型稀土-镍系贮氢合金,人们的研究开发多集中在B侧方面,而对于A侧则研究甚少。荷兰菲利浦公司(J.J.G.Willems,Philips J.Res.1984.39 Suppl)首先采用不同的合金元素分别替代二元合金LaNi5中的La和Ni,力求通过减小电极材料吸氢时体积膨胀以提高电极在充放电过程中的稳定性,结果优选出合金材料La0.8Nd0.2Ni2.5Co2.4Si0.1,该材料的起始容量为290mAh/g,经1000次充放电循环后,容量仅下降30%。
众所周知,La和Co价格较高,实用化的电极材料应减少合金中La和Co的含量,而采用混合稀土金属取代纯La,并适当降低Co含量是一条可行的合金化途径。然而,市售的混合稀土金属原材料却受到其产地和提取方法的限制。在混合稀土金属中主要含有La、Ce、Nd、Pr等稀土组元,按其产地和提取方法的不同可分为富镧混合稀土、富铈混合稀土、高镧混合稀土,相应形成富镧混合稀土合金、富铈混合稀土合金、高镧混合稀土合金三大系列。研究表明,混合稀土金属中的La、Ce、Nd、Pr元素的含量及比例对贮氢合金的性能有重要的影响,如在富铈混合稀土合金中,平衡氢压随La含量增加而降低,但随Ce、Nd增加而升高;充电效率、起始容量、荷电保持能力及循环寿命均随La含量增加而改善,而Ce、Nd的作用则相反;适当的Nd含量使合金的抗腐蚀性能得到提高。
各种混合稀土金属La、Ce、Nd、Pr的含量(重量百分比):混合稀土种类 La Ce Nd Pr富镧混合稀土Ml 44~51 3~5 24~41 9~11富铈混合稀土Mm 20~24 50~56 15~17 5~6高镧混合稀土LM 80 3 10 5
本发明的目的在于提供一种稀土系贮氢合金电极材料,在对合金中混合稀土组元La、Ce、Nd、Pr进行优化配置的基础上,提出一种化学式为MlαMm1-αNi5-x-y-zCoxMnyTiz的贮氢合金,式中0<α<1.0,x=0.5~1.0,y=0.3~0.6,z=0.01~0.1;由该合金制成综合性能优异、符合实用化要求的贮氢合金电极材料。
为实现本发明的目的,采取如下技术措施:
1.对稀土系RE(NiCoMnTi)5贮氢合金中的RE稀土组元La、Ce、Nd、Pr作系统的优化研究,提出等放电容量分布图、等循环寿命比较图,评估稀土组元La、Ce、Nd、Pr对贮氨合金性能的影响;
2.在适当调整La、Ce、Nd、Pr的含量及比例基础上,同时采用富镧混合稀土金属和富铈混合稀土金属作为原材料,获得综合性能优异的贮氨合金电极材料。
本发明的贮氢合金电极材料,含有混合稀土金属元素,其特征是它的化学式为MlαMm1-αNi5-x-y-zCoxMnyTiz,式中0<α<1,x=0.5~1.0,y=0.3~0.6,z=0.01~0.1。
上述贮氢合金电极材料,其优先选用的化学式为:Ml0.85Mm0.15Ni3.8Co0.75Mn0.4Ti0.05,式中:Ni、Co、Mn、Ti纯度皆为99wt%;富镧混合稀土金属Ml的牌号为RELa-40,富铈混合稀土金属Mm的牌号为RECe-50。在Ml中,稀土金属总含量不小于98wt%,La含量44~51wt%,Ce含量3~5wt%,Nd含量27~41wt%,Pr含量9~11wt%;在富铈混合稀土金属Mm中稀土金属总含量不低于99wt%,La含量20~24wt%,Ce含量50~56wt%,Nd含量15~17wt%,Pr含量5~6wt%。
制备该贮氢合金时,将上述金属原材料按化学式配比称重,置于真空感应炉的氧化铝坩埚内,经抽空排气,在氩气保护下熔炼,浇注成铸锭。破碎后装入耐压反应容器,经气态吸放氢循环粉碎至300~500目合金粉末。将合金粉末分别制成贮氢合金测试电极和电池电极。
同现有技术比较,本发明具有如下优点:
1.在稀土系AB5型多元贮氢合金设计过程中,在对B侧多元合金元素进行优化配置的同时,着重对A侧的稀土金属组元La、Ce、Nd、Pr中每一个组元对合金电化学性能的影响作了深入研究,进行系统的优化组合,在合理确定La、Ce、Nd、Pr各自的含量和比例的基础上,采用合理配比的富镧混合稀土金属Ml和富铈混合稀土金属Mm取代,设计出一种性能优异的稀土系贮氢合金,作为氢化物-镍蓄电池负极活性材料。
2.材料的起始容量、同等次数放电后容量保持率优于现有技术。在同等的充放电条件下,电池的放电容量比现有技术提高10%以上。
3.电池封口后经1~3次活化,即可达到标准要求的放电容量指标。表1为本发明与现有技术性能比较数据。
图1为贮氢合金RE(NiCoMnTi)5的等放电容量分布图。合金化学式中RE=La0.5-dCedNdePr0.5-e,充电电流为30mA/g,充电时间为16小时,放电电流为60mA/g。
图2、图3为含有稀土金属La、Ce、Nd、Pr的贮氢合金的等循环寿命比较图,采用与图1相同的合金,充电400mA/g×1hr,放电240mA/g。图形2的循环充放电50次;图形3循环充放电250次。
实施例1:
制造化学式为ML0.85Mm0.15Ni3.8Co0.75Mn0.4Ti0.05贮氢合金,原材料Ml采用牌号RELa-40,Mm中稀土金属总含量为99wt%,Ce含量55wt%,La含量23wt%,Nd含量15wt%,Pr含量6wt%,将上述金属原材料按化学式配比称重,干燥后置于真空感应熔炼炉的氧化铝坩埚内,经抽空排气,在氩气保护下熔炼并浇注成铸锭,铸锭破碎后装入耐压反应器,经气态吸放氢循环粉碎至300~500目粉末。将合金粉末与3%PVA溶液调制成糊状,充填在泡沫镍基板内,经滚压减薄成厚度为0.4mm,干燥后作为贮氢合金负极。在开口电解池中配以氧化镍为正极,以Hg/HgO电极为参比电极,6M KOH为电解液。用30mA/g合金的电流密度恒流充电16小时,然后分别以60mA/g合金、600mA/g合金放电倍率放电,测量贮氢合金的电化学容量C1和C2,以C2/C1表示高倍率放电下的高速放电能力。贮氢合金循环寿命用大电流放电循环来评价,充电电流400mA/g,放电电流240mA/g,测试经300次、850次大电流放电循环后合金电化学容量的保持率(%),放电过程的截止电位为-600mv。
测试结果:未经表面处理的合金,其起始容量为280mAh/g,反映出高倍率放电性能的C2/C1为91.5%,经850次大电流循环放电后容量保持率为73%,说明该贮氢合金具有良好的综合性能。
为便于比较,采用贮氢合金粉末与电解铜粉按1∶2比例混合压成片电极,作常规充放电测试,其放电容量为316mAh/g。
实施例2:
按照实施例1的方法制成贮氢合金负极,以氧化镍为正极,尼龙无纺布为隔膜,以6MKOH+1MLiOH为电解液,装配成AA型密封Ni/MH试验电池,封口后经1~3次活化即可达到标准的放电容量指标,在不同的放电倍率下,测得电池的放电容量为:
放电倍率 0.2C 1C 2C 3C 5C
放电容量(mAh) 1340 1140 1050 986 930
上述电池按IEC标准测试循环工作寿命,其循环工作寿命不低于500周。
表1
注:(1)
序号 | 技术方案 | 稀土类型 | 起始容量mAh/g | 300次放电后容量保持率 | 高速放电能力C:300mA/gC:20mA/g | 活化能力 |
1 | EP271043 | 富铈 | 254 | 85% | ≤43% | 5~7次 |
2 | JP03-274240 | 高镧 | 286 | 71~89% | 59~77% | 3~4次 |
3 | CN94112039 | 富镧 | 305 | 89.6% | 83.83% | 3次 |
4 | 本发明 | 配置 | 316 | 81~90% | 91.5% | 2~3次 |
序号1方案合金为MmNi3.55Co0.75Mn0.4Al0.3
序号2方案合金为Lm0.95Zr0.05Ni4.0Co0.5Al0.5
序号3方案合金为MlNi3.45Co1.0Mn0.5Ti0.05
序号4方案合金为Ml0.85Mm0.15Ni3.8Co0.75Mn0.4Ti0.05
(2)各种性能在同等条件下充放电比较。
Claims (2)
1.一种贮氢合金电极材料,含有混合稀土金属,其特征在于:它的化学式为RENi5-x-y-zCoxMnyTiz,式中RE=MlαMm1-α,0<α<1,x=0.5~1.0,y=0.3~0.6,z=0.01~0.1。
2.根据权利要求1的贮氢合金电极材料,其特征在于:它的化学式为Ml0.85Mm0.15Ni3.8Co0.75Mn0.4Ti0.05。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529426A (en) * | 1983-07-22 | 1985-07-16 | At&T Bell Laboratories | Method of fabricating high birefringence fibers |
EP0407591A1 (en) * | 1988-10-11 | 1991-01-16 | Oki Electric Industry Co., Ltd. | Differential amplifier circuit |
EP0439918A1 (en) * | 1989-12-29 | 1991-08-07 | AT&T Corp. | Method for manufacturing an article comprising a refractory dielectric body |
JPH03289042A (ja) * | 1990-04-02 | 1991-12-19 | Agency Of Ind Science & Technol | 水素吸蔵電極 |
EP0484659A2 (en) * | 1990-11-09 | 1992-05-13 | Corning Incorporated | Method of making polarization retaining fiber |
JPH04253158A (ja) * | 1991-01-29 | 1992-09-08 | Japan Storage Battery Co Ltd | 水素吸蔵電極の製造方法 |
CN1078827A (zh) * | 1992-05-16 | 1993-11-24 | 上海工业大学 | 一种贮氢电极合金 |
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4529426A (en) * | 1983-07-22 | 1985-07-16 | At&T Bell Laboratories | Method of fabricating high birefringence fibers |
EP0407591A1 (en) * | 1988-10-11 | 1991-01-16 | Oki Electric Industry Co., Ltd. | Differential amplifier circuit |
EP0439918A1 (en) * | 1989-12-29 | 1991-08-07 | AT&T Corp. | Method for manufacturing an article comprising a refractory dielectric body |
JPH03289042A (ja) * | 1990-04-02 | 1991-12-19 | Agency Of Ind Science & Technol | 水素吸蔵電極 |
EP0484659A2 (en) * | 1990-11-09 | 1992-05-13 | Corning Incorporated | Method of making polarization retaining fiber |
JPH04253158A (ja) * | 1991-01-29 | 1992-09-08 | Japan Storage Battery Co Ltd | 水素吸蔵電極の製造方法 |
CN1078827A (zh) * | 1992-05-16 | 1993-11-24 | 上海工业大学 | 一种贮氢电极合金 |
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