CN1027980C - 储氢合金电极的活性材料 - Google Patents
储氢合金电极的活性材料 Download PDFInfo
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- CN1027980C CN1027980C CN92100029A CN92100029A CN1027980C CN 1027980 C CN1027980 C CN 1027980C CN 92100029 A CN92100029 A CN 92100029A CN 92100029 A CN92100029 A CN 92100029A CN 1027980 C CN1027980 C CN 1027980C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/383—Hydrogen absorbing alloys
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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
- 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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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S420/00—Alloys or metallic compositions
- Y10S420/90—Hydrogen storage
Abstract
本发明属于储氢合金电极用的活性物质材料,选择的化学组成为MmNi5-x-y-x-uAxByCzDu,其中D=Li、Na、K、u的大小视合金具体组成而定为大于零的数。这种活性物质材料在碱蓄电池的充放电过程中可以不断地放出碱金属离子M+,从电池内部增加MOH的浓度,起到有效地保护电池正极和负极的作用,提高了电池的循环使用寿命和放电容量。
Description
本发明涉及在由活性材料组成的电极中活性物质材料的选择。
二十多年来人们一直在致力于对可以用来制造储氢合金电极的活性物质材料进行选择的研究工作。最初选用的是LaNi5合金(1),由于由LaNi5合金制成的电极组装成的碱蓄电池的寿命极短,所以后来人们对它的组成结构进行了不断的改进。例如,用Co取代LaNi5中的部分Ni,研制成LaNi5-xCox3元合金(a);近期最有代表性的改进是组成为MmNi3.8Co0.5Mn0.4Al0.3的5元合金(4).(5)。然而时至今日,由上述各种LaNi5系合金,或钛系合金,或锆系合金,或钙系合金制成电极组装的碱蓄电池的循环使用寿命仍不理想。
经过分析发现,其原因并不都在于储氢合金负极的活性材料本身的稳定性,还与这类碱蓄电池的氧化镍正极在充放电过程中会受到电解液的腐蚀有关,并且随着充放电次数的增加腐蚀反应会加剧。一般采取的措施是在电池密封之前在电解液KOH中加入一定比例的LiOH,用以保护正极。但这一保护措施的效果不能令人满意。如果随着电池充放电过程的循环进行,电解液中LiOH的浓度也能够随之增加,那么保护正极的效果将会得到明显提高,电池循环使用的寿命也就会大大延长。然而想在电池密封之后充放电使用过程中随时从外向里再添加LiOH是不可能实施的。
本发明的任务是提出一种新型的储氢合金活性材料,用这种活性材料制成碱蓄电池的负极在电池的充放电过程中可以不断地放出碱金属离子M+(特别是Li+),从电池内部不断地增加MOH(特别是LiOH)的浓度,从而明显地提高对电池正极的保护效果,也就延长了电池的循环使用寿命。
本发明的任务是通过进一步改进储氢合金材料的组成结构来实现的。在现有各种系列的储氢合金材料中加入碱金属元素而形成具有下列组成形式的合金:GDu,其中G为现有的各种系列的合金,如稀土系(LaNi5等)、钛系(TiNi等)、钙系(CaNi5等)、锆系(ZrMn2等),D=Li、Na、K、u的大小视合金具体组成而定,例如,在已有稀土合金MmNi5-x-y-z-uAxByCz中加入碱金属元素形成具有下列组成的合金:MmNi5-x-y-z-uAxByCzDu,其中Mm为混合稀土,A=Mn、S、V,B=Cr、Co=Ti、Nb、Zr、Si,C=Al、Mg、Ca,D=Li、Na、K,O<X≤0.5,O<Y≤0.4,O<u≤0.9。由于碱金属Li、Na、K的加入,改善了合金的结构,碱金属可与Ni、Mn、Al等元素形成多种稳定的合金相,并部分分散于合金晶界中,处于相界缺陷处的碱金属原子,当用该合金制成的电极浸入电解液中时会首先被氧化形成氢氧化物,而正是这种氢氧化物(特别是LiOH)对电池的正极有保护作用,随着电池充放电过程的循环进行,该合金中的碱金属原子不断地转变成为氢氧化物,也就不断地增加了氢氧化物的浓度,这就进一步提高了对正极的保护效果。与此同时,在储氢合金负极表面形成的氢氧化物分布于合金表面的缺陷位置上,也保护了储氢合金结构内部不被氧化,因而大大提高了电池的循环使用寿命。由于合金结构的改善和在充放电过程中形成的MOH有较高的活性,在提高电池循环使用寿命的同时也提高了该储氢合金材料的催化活性和电化学容量,经气固反应实验表明该合金的平台压力适中。
本发明的储氢合金活性材料是在真空感应炉中制作,碱金属形成中间合金,保证合金中加入成分的稳定性。
本发明与现有技术相比,用本发明活性材料制成的电极组装的碱蓄电池的循环使用寿命可延长2~3倍,常温放电容量和能量密度明显提高(见附表1),高倍率放电性能进一步提高(见附表2),只需经3~5次“活化”处理即可达到充放电容量的最大值(见附表3)
实施例1
将在真空感应炉中制成的组成为MmNi3.8
Co0.5Mn0.4Al0.2Li0.1的储氢合金活性材料用振磨法磨成38~50μm目的粉末,用100∶8重量的PTFE溶液调成糊状物,在60℃下经多次滚压成0.4mm厚度的合金片将该合金片用100MPa的压力压在适当大小的(据电池外壳尺寸而定)导电镍基底的一侧制成合金电极以该电极为负极,氧化镍为正极,5mKOH+1mLiOH溶液为电解液,尼龙无纺布为隔膜装配成AA型密封碱蓄电池(A),按IEC标准做循环使用寿命实验,经200次循环充放电后电池容量仅下降3.6%,平均每次循环周期容量下降率为0.018%,而用组成为MmNi3.8Co0.5Mn0.4Al0.3的合金按同样工艺组装成同型号的碱蓄电池(B),在同样测试条件下,经200次循环充放电后电池容量下降8.4%,平均下降率为0.042%附表1中列出了电池A与电池B的放电容量和能量密度的对照数据
实施例2
将组成为MmNi3.0Mn0.4Co0.5Al0.2Li0.9的储氢合金活性材料用振磨机磨成38~50μm粉末,用2%PVA溶液调成糊状,将1克该合金粉末涂在2×2(cm2)的厚度为1.2mm的泡沫镍片上,用200MPa压力压片制成储氢合金电极(C)。以该合金电极为负极放入5MKOH溶液中,以氧化镍为正极,Hg/HgO电极为参比电极,用0.1C充电16小时,以不同放电倍率放电,测其电化学容量,并与组成为MmNi3.8Co0.5Mn0.4Al0.3的储氢合金活性材料制成的电极(B)对照,附表2列出对比数据
附表2 两种合金材料负极放电容量对比数据(1克合金)
放电倍率 0.2C 1C 3C 5C
放电 C 302 266 242 220
容量 B 290 254 231 206
实施例3
将在真空感应炉中制成的组成为MmNi3.4Co0.5Mn0.3Al0.1Li0.8的储氢合金活性材料按实施例1的工艺操作制成AA型密封碱蓄电池(D),在其封口后仅需3次“活化”即可达到标准要求的放电容量指标,比电池(B)的“活化”次数缩短3倍附表3列出电池(D)与电池(B)的“活化”次数的对比数据
参考文献
(1)Kujiperrs,F.A.,Thesis,University of Technology,1973.
(2)Williums,Philips Journal of Research1984,39,Supplement1
(3)Chiaki Iwakura,Journal of the Less-Common Metal,1990,159,127
(4)JP63-175339
(5)JP63-264869
附表1 两种活性材料组装的AA型碱蓄电池放电容量和能量密度对照数据
放电倍率 放电容量(mAh) 能量密度
Wh/Kg Wh/L
A B A B A B
0.2C 1236 1148 58.9 55.4 192.0 175.5
1C 1070 1048 51.0 50.3 166.3 158.6
3C 966 956 45.5 45.3 148.6 147.8
5C 912 911 43.1 43.1 141.8 141.2
附表3 两种活性材料组装的AA型碱蓄电池“活化”次数对照数据
放电次数 1 2 3 4 5 6 7 8 9 10 11 12
放电 D 930 974 1076 1117 1120 1134 1150 1154 1174 1200 1202 1202
容量
mAh B 570 760 820 848 836 916 932 967 990 1010 1023 1023
Claims (2)
1、一种储氢合金电极用的活性物质材料,其特征在于化学组成选择为MmNi5-x-y-x-uAxByCzDu,其中Mm为混合稀土,A=Mn、Sn、V,B=Co、Ti、Zr、C=Al、Mg、Ca,D=Li、Na、K,O<Y≤0.5,O<Z≤0.4,0<u≤0.9。
2、按照权利要求1所述的化学组成为Mm Ni5-x-y-z-uAxByCzDu的活性物质材料,其特征在于D=Li,O<u≤0.9。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN92100029A CN1027980C (zh) | 1992-01-08 | 1992-01-08 | 储氢合金电极的活性材料 |
US07/862,105 US5242656A (en) | 1992-01-08 | 1992-04-02 | Active material of hydrogen storage alloy electrode |
EP92311097A EP0554617B1 (en) | 1992-01-08 | 1992-12-04 | Active material of hydrogen storage alloy electrode |
DE69209044T DE69209044T2 (de) | 1992-01-08 | 1992-12-04 | Aktives Material von einer Elektrode aus Wasserstoffspeicherlegierung |
CA002085035A CA2085035A1 (en) | 1992-01-08 | 1992-12-10 | Active material of hydrogen storage alloy electrode |
JP5017066A JPH0676818A (ja) | 1992-01-08 | 1993-01-07 | 水素貯蔵合金電極の活性物質 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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CN92100029A CN1027980C (zh) | 1992-01-08 | 1992-01-08 | 储氢合金电极的活性材料 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1064174A CN1064174A (zh) | 1992-09-02 |
CN1027980C true CN1027980C (zh) | 1995-03-22 |
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CN92100029A Expired - Fee Related CN1027980C (zh) | 1992-01-08 | 1992-01-08 | 储氢合金电极的活性材料 |
Country Status (6)
Country | Link |
---|---|
US (1) | US5242656A (zh) |
EP (1) | EP0554617B1 (zh) |
JP (1) | JPH0676818A (zh) |
CN (1) | CN1027980C (zh) |
CA (1) | CA2085035A1 (zh) |
DE (1) | DE69209044T2 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1050154C (zh) * | 1996-07-11 | 2000-03-08 | 南开大学 | 球形的储氢合金及其制造方法 |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1028882C (zh) * | 1992-07-16 | 1995-06-14 | 南开大学 | 新型储氢合金电极材料 |
US5547784A (en) * | 1993-01-18 | 1996-08-20 | Matsushita Electric Industrial Co., Ltd. | Alkaline storage battery and method for producing the same |
US5501917A (en) * | 1994-01-28 | 1996-03-26 | Hong; Kuochih | Hydrogen storage material and nickel hydride batteries using same |
US5733680A (en) * | 1994-01-28 | 1998-03-31 | Hong; Kuochih | Method for making hydride electrodes and hydride batteries suitable for various temperatures |
US5512385A (en) * | 1994-02-28 | 1996-04-30 | Matsushita Electric Industrial Co., Ltd. | Hydrogen storage alloy and nickel-metal hydride storage battery using the same |
US5552246A (en) * | 1994-03-14 | 1996-09-03 | Hong; Kuochih | Materials for hydrogen storage, hydride electrodes and hydride batteries |
US5695530A (en) * | 1994-03-14 | 1997-12-09 | Hong; Kuochih | Method for making high charging efficiency and fast oxygen recombination rechargeable hydride batteries |
JP3365577B2 (ja) * | 1994-05-27 | 2003-01-14 | 松下電器産業株式会社 | 密閉形ニッケル−水素蓄電池の単電池および単位電池 |
JPH0869796A (ja) * | 1994-08-22 | 1996-03-12 | Hon Kuochii | 水素保存材料、水素化物電極、水素保存装置、及びニッケル−水素化物電池 |
US5662729A (en) * | 1994-10-04 | 1997-09-02 | Sanyo Electric Co., Ltd. | Shaped body of hydrogen absorbing alloy and container packed with hydrogen absorbing alloy |
US6110304A (en) * | 1995-11-17 | 2000-08-29 | Sanyo Electric Co., Ltd. | Hydrogen-absorbing alloy electrode for alkaline storage batteries |
DE69839140T2 (de) * | 1997-06-17 | 2008-06-19 | Kabushiki Kaisha Toshiba, Kawasaki | Wasserstoffabsorbierende Legierung |
US6375869B1 (en) | 1999-01-29 | 2002-04-23 | Santoku Corporation | AB5-type rare earth transition intermetallic compounds for the negative electrodes of rechargeable batteries |
US6524745B1 (en) * | 1999-05-19 | 2003-02-25 | Energy Conversion Devices, Inc. | Electrochemically stabilized CaNi5 alloys and electrodes |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4623597A (en) * | 1982-04-28 | 1986-11-18 | Energy Conversion Devices, Inc. | Rechargeable battery and electrode used therein |
US4605603A (en) * | 1983-12-26 | 1986-08-12 | Kabushiki Kaisha Toshiba | Hermetically sealed metallic oxide-hydrogen battery using hydrogen storage alloy |
US4952465A (en) * | 1986-04-30 | 1990-08-28 | The Standard Oil Company | Additive for energy storage devices that evolve oxygen and hydrogen |
NL8801233A (nl) * | 1988-05-11 | 1989-12-01 | Philips Nv | Gesloten elektrochemische cel. |
-
1992
- 1992-01-08 CN CN92100029A patent/CN1027980C/zh not_active Expired - Fee Related
- 1992-04-02 US US07/862,105 patent/US5242656A/en not_active Expired - Fee Related
- 1992-12-04 EP EP92311097A patent/EP0554617B1/en not_active Expired - Lifetime
- 1992-12-04 DE DE69209044T patent/DE69209044T2/de not_active Expired - Fee Related
- 1992-12-10 CA CA002085035A patent/CA2085035A1/en not_active Abandoned
-
1993
- 1993-01-07 JP JP5017066A patent/JPH0676818A/ja active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1050154C (zh) * | 1996-07-11 | 2000-03-08 | 南开大学 | 球形的储氢合金及其制造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN1064174A (zh) | 1992-09-02 |
CA2085035A1 (en) | 1993-07-09 |
DE69209044T2 (de) | 1996-10-31 |
EP0554617B1 (en) | 1996-03-13 |
EP0554617A1 (en) | 1993-08-11 |
JPH0676818A (ja) | 1994-03-18 |
US5242656A (en) | 1993-09-07 |
DE69209044D1 (de) | 1996-04-18 |
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