JPH04245165A - Hydrogen absorbing alloy electrode - Google Patents
Hydrogen absorbing alloy electrodeInfo
- Publication number
- JPH04245165A JPH04245165A JP3032222A JP3222291A JPH04245165A JP H04245165 A JPH04245165 A JP H04245165A JP 3032222 A JP3032222 A JP 3032222A JP 3222291 A JP3222291 A JP 3222291A JP H04245165 A JPH04245165 A JP H04245165A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- iron
- storage alloy
- electrode
- capacity
- 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.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000003860 storage Methods 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 150000002506 iron compounds Chemical class 0.000 claims description 8
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- -1 ferrous compound Chemical class 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 229910001021 Ferroalloy Inorganic materials 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000000843 powder Substances 0.000 description 12
- 239000002184 metal Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020854 La(OH)3 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
Description
【0001】0001
【産業上の利用分野】本発明は、ニッケル−水素蓄電池
の負極として用いられる水素吸蔵合金電極の改良に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvements in hydrogen storage alloy electrodes used as negative electrodes for nickel-hydrogen storage batteries.
【0002】0002
【従来の技術】近年、エレクトロニクス機器の軽量化に
対する要望は著しく、機器の一部をなす電池も例外でな
く、よりエネルギー密度の高い小型軽量の電池へ移りつ
つある。その一つとしてニッケル−カドミウム電池より
もエネルギー密度の高いニッケル−水素蓄電池が望まれ
ている。BACKGROUND OF THE INVENTION In recent years, there has been a significant demand for lighter electronic equipment, and batteries that form part of these equipment are no exception, with a shift toward smaller, lighter batteries with higher energy density. As one of these, nickel-hydrogen storage batteries, which have a higher energy density than nickel-cadmium batteries, are desired.
【0003】ところで、ニッケル−水素蓄電池の実用化
において最も重要な因子は、水素吸蔵合金の腐食を防止
し、サイクル寿命を長くさせることである。そういう観
点より今までに、水素吸蔵合金の表面を耐食性のニッケ
ル、銅などの金属で被覆することが提案されている(特
開昭61−64069号、特開昭61−101957号
)。合金粉末へのこれらの金属の被覆方法は、自己触媒
型の湿式無電解めっき法などによって行なわれる。By the way, the most important factor in the practical application of nickel-hydrogen storage batteries is to prevent corrosion of the hydrogen storage alloy and to extend the cycle life. From this point of view, it has been proposed to coat the surface of hydrogen storage alloys with corrosion-resistant metals such as nickel and copper (Japanese Patent Laid-Open Nos. 61-64069 and 61-101957). The alloy powder is coated with these metals by autocatalytic wet electroless plating or the like.
【0004】然るに合金粉末に金属箔を被覆するという
ことは、作業の工程の面で繁雑化するという欠点を有す
る。無電解めっき法を例にとれば、めっき液に含浸、攪
拌、ろ過、水洗乾燥などの工程が必要であり、めっき後
の廃液の処理などを考えると、製造のコストアップにつ
ながるという問題がある。However, coating the alloy powder with metal foil has the disadvantage of complicating the work process. Taking electroless plating as an example, processes such as impregnation, stirring, filtration, washing and drying are required in the plating solution, and when considering the treatment of waste solution after plating, there is a problem in that it leads to increased manufacturing costs. .
【0005】又、めっき後の重量でエネルギー密度を考
えると、めっき層自体は容量に寄与しないので、エネル
ギー密度の低下を招くという問題もある。[0005] Furthermore, when considering the energy density in terms of the weight after plating, there is also the problem that the plating layer itself does not contribute to the capacity, leading to a decrease in the energy density.
【0006】[0006]
【発明が解決しようとする課題】本発明は上記従来の問
題点に鑑みなされたものであり、製造の工程を簡略化し
、高容量化、サイクルの長寿命化を図ることができる水
素吸蔵合金電極を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above conventional problems, and provides a hydrogen storage alloy electrode that can simplify the manufacturing process, increase capacity, and extend cycle life. It provides:
【0007】[0007]
【課題を解決するための手段】本発明は上記課題を達成
すべく、電気化学的に水素の吸蔵・放出を繰り返すこと
が可能な水素吸蔵合金粉末に、鉄、鉄の合金又は鉄の化
合物の粉末のうち少なくとも1種以上を0.01〜20
wt%混合した水素吸蔵合金電極であり、鉄の化合物が
、鉄の酸化物、水酸化物、塩である水素吸蔵合金電極で
ある。[Means for Solving the Problems] In order to achieve the above-mentioned problems, the present invention provides hydrogen storage alloy powder capable of electrochemically absorbing and desorbing hydrogen repeatedly, using iron, an iron alloy, or an iron compound. At least one kind of powder from 0.01 to 20
This is a hydrogen storage alloy electrode in which the iron compound is an iron oxide, hydroxide, or salt.
【0008】[0008]
【作 用】混合した鉄、鉄の合金又は鉄の化合物の粉
末のうち少なくとも1種以上の物質が、水素吸蔵合金電
極内に分散し、水素吸蔵合金の腐食を防止し、かつ粒子
間の導電性を保つ働きをすることにより、高容量でサイ
クル寿命特性が向上した水素吸蔵合金電極を実現できる
。[Function] At least one of the mixed powders of iron, iron alloys, or iron compounds is dispersed within the hydrogen storage alloy electrode to prevent corrosion of the hydrogen storage alloy and conductivity between particles. By acting to maintain the properties, hydrogen storage alloy electrodes with high capacity and improved cycle life characteristics can be realized.
【0009】[0009]
【実施例】以下、本発明の詳細について説明する。水素
吸蔵合金とその電極は、以下の方法で作製した。Laと
、Ni,Alの各成分元素を高周波溶解炉で溶解し、L
aNi4.3 Al0.7 の組成比の水素吸蔵合金を
作製した。この合金をアルゴン雰囲気下で熱処理した後
、200メッシュ以下に粉砕し、水素吸蔵合金粉末を得
た。この水素吸蔵合金に対しFe粉末を10wt%混合
した後、ポリビニルアルコールの3wt%の水溶液でペ
ースト状とした。ついで、このペーストを多孔度95%
のニッケル多孔体に充填し、真空乾燥後加圧して電極(
1)を作製した。FeO粉末を混合したものについても
同様の方法で電極を(2)を作製した。EXAMPLES The details of the present invention will be explained below. The hydrogen storage alloy and its electrode were produced by the following method. Each component element of La, Ni, and Al is melted in a high frequency melting furnace, and L
A hydrogen storage alloy having a composition ratio of aNi4.3 Al0.7 was produced. This alloy was heat treated in an argon atmosphere and then ground to 200 mesh or less to obtain a hydrogen storage alloy powder. This hydrogen storage alloy was mixed with 10 wt % Fe powder and then made into a paste with a 3 wt % aqueous solution of polyvinyl alcohol. Next, this paste was made to have a porosity of 95%.
Filled with nickel porous material, vacuum dried and then pressurized to form an electrode (
1) was produced. An electrode (2) was also produced using a mixture of FeO powder in the same manner.
【0010】この様に作製した水素吸蔵合金電極を負極
として、対極には、負極容量より大なるニッケル電極を
用いて、比重1.24のKOH電解液中で充放電し、水
素吸蔵合金電極の電気化学的容量を測定した。The hydrogen storage alloy electrode prepared in this manner was used as a negative electrode, and a nickel electrode having a larger capacity than the negative electrode was used as the counter electrode, and the hydrogen storage alloy electrode was charged and discharged in a KOH electrolyte having a specific gravity of 1.24. The electrochemical capacity was measured.
【0011】充電は0.1Cで150%、放電は0.2
Cで電池電圧が1Vまで行なった。図1に上記に示した
電気化学的容量のサイクル変化を示す。水素吸蔵合金だ
けの電極(3)は、短いサイクルで容量の低下をきたす
。水素吸蔵合金電極の劣化は、合金表面に析出した腐食
生成物、たとえば、La(OH)3 の様な導電性の無
い物質によって、合金粒子間の電子移動が不可能になる
ためではないかと考えられる。[0011] Charging is 150% at 0.1C, discharging is 0.2
C until the battery voltage reached 1V. FIG. 1 shows the cycle change in the electrochemical capacity shown above. The electrode (3) made of only a hydrogen storage alloy suffers from a decrease in capacity in short cycles. The deterioration of hydrogen storage alloy electrodes is thought to be due to corrosion products deposited on the alloy surface, such as non-conductive substances such as La(OH)3, which make electron transfer between alloy particles impossible. It will be done.
【0012】次に導電性を確保するために導電助剤とし
てNi粉末を水素吸蔵合金に対し10wt%混合して電
極(4)を作製した。その結果、図1に示すようにサイ
クルに対する容量の変化は1サイクル目の容量を保つと
いう経過を示した。Next, in order to ensure conductivity, an electrode (4) was prepared by mixing 10 wt % of Ni powder as a conductive aid with the hydrogen storage alloy. As a result, as shown in FIG. 1, the change in capacity with respect to cycles showed a progression in which the capacity at the first cycle was maintained.
【0013】これに対し、Feを混合した電極(1)は
、サイクルを繰り返す毎に容量が増大し10サイクル以
降になって一定の容量を示すようになる。On the other hand, the capacity of the electrode (1) containing Fe increases each time the cycle is repeated, and it shows a constant capacity after the 10th cycle.
【0014】FeOを混合した電極(2)は、3サイク
ルまで容量が増大し以降一定となる。それらの原因を次
のように考えている。ニッケルは、電解液中における電
池作動電位において、耐食性のある金属である。[0014] The capacity of the electrode (2) containing FeO increases until the third cycle and then becomes constant. I think the reasons for these are as follows. Nickel is a corrosion-resistant metal at the cell operating potential in the electrolyte.
【0015】しかし鉄は、サイクル中に溶解析出を繰り
返す金属であるところが大きな特徴である。よって混合
した鉄は、水素吸蔵合金粉末がサイクル中に微粉化して
新しい反応面を形成したとしても、そこでまた金属とし
て析出し、微粉化した水素吸蔵合金粉末の集電をするの
で利用率を高めることができると考えられる。つまり、
FeやFeOの混合物は、電極内にサイクルが進むにつ
れて分散していくため集電能力が増大し、初期の容量が
増大していくものだと考えられる。Fe,FeOの初期
サイクルにおける容量増加のスピードの差は、電解液中
への溶解度の差であると考えられる。サイクルを繰り返
しても容量が低下しないのは、析出した鉄が腐食生成物
を覆い巻き込みながら、導電性ネットワークを形成する
ものと考えられるからである。また、析出した鉄によっ
て合金の腐食が抑制されているとも考えられる。実際サ
イクル後の電極のSEMで観察すると腐食が抑制されて
いることが観察できる。However, a major feature of iron is that it is a metal that undergoes repeated melting and precipitation during cycles. Therefore, even if the hydrogen storage alloy powder is pulverized during the cycle and forms a new reaction surface, the mixed iron will precipitate there again as a metal and collect the current of the pulverized hydrogen storage alloy powder, increasing the utilization rate. It is thought that it can be done. In other words,
It is thought that the mixture of Fe and FeO is dispersed within the electrode as the cycle progresses, increasing the current collecting ability and increasing the initial capacity. The difference in the speed of capacity increase in the initial cycle between Fe and FeO is thought to be due to the difference in solubility in the electrolyte. The reason why the capacity does not decrease even after repeated cycles is thought to be that the precipitated iron forms a conductive network while covering and enveloping the corrosion products. It is also believed that the precipitated iron suppresses corrosion of the alloy. In fact, when the electrodes are observed by SEM after cycling, it can be seen that corrosion is suppressed.
【0016】したがって充放電中に鉄の錯イオンを生成
し、鉄として電極中に析出できるものであれば、鉄の化
合物が鉄の酸化物、水酸化物、塩であっても以上述べた
効果を期待できる。鉄、鉄の合金又は鉄の化合物の粉末
のうち少なくとも1種以上の混合量は、水素吸蔵合金に
対して0.01wt%の混合量からその効果が現れ、2
0wt%付近より効果が飽和することから0.01〜2
0wt%の範囲で混合される必要がある。Therefore, as long as iron complex ions are generated during charging and discharging and can be deposited as iron in the electrode, the above-mentioned effects can be achieved even if the iron compound is an iron oxide, hydroxide, or salt. You can expect. The mixing amount of at least one kind of iron, iron alloy, or iron compound powder becomes effective from a mixing amount of 0.01 wt% with respect to the hydrogen storage alloy.
Since the effect is saturated around 0wt%, it is 0.01 to 2.
It is necessary to mix within the range of 0wt%.
【0017】なお、本実験においての混合方法は、物理
混合であったが、しかしマイクロカプセルなど他の混合
方法でも同様の効果を期待できる。ただ製造工程を簡略
化できる点で物理混合は都合が良い。Although the mixing method used in this experiment was physical mixing, similar effects can be expected with other mixing methods such as microcapsules. However, physical mixing is advantageous in that it can simplify the manufacturing process.
【0018】また、本実験では、ニッケル多孔体基板を
用いたが、本発明はこれに限らず、エキスパンドメタル
、メタルメッシュ、ニッケルめっきパンチングメタル等
を基板として用いることもできる。Further, in this experiment, a nickel porous substrate was used, but the present invention is not limited to this, and expanded metal, metal mesh, nickel-plated punching metal, etc. can also be used as the substrate.
【0019】[0019]
【発明の効果】上述したごとく、本発明はエネルギー密
度が高く、長寿命の水素吸蔵電極を、鉄、鉄の合金又は
鉄の化合物の粉末をただ混合するだけで提供することが
できるので、その工業的価値は極めて大である。[Effects of the Invention] As described above, the present invention can provide a hydrogen storage electrode with high energy density and long life by simply mixing powders of iron, iron alloys, or iron compounds. The industrial value is extremely large.
【図1】サイクル数と負極容量との関係を示す図である
。FIG. 1 is a diagram showing the relationship between the number of cycles and negative electrode capacity.
1 Feを10wt%添加した電池
2 FeOを10wt%添加した電池3 無添加の
電池
4 Niを10wt%添加した電池1 Battery with 10 wt% of Fe added 2 Battery with 10 wt% of FeO added 3 Battery with no additives 4 Battery with 10 wt% of Ni added
Claims (2)
の化合物のうち少なくとも1種以上を0.01〜20w
t%混合した水素吸蔵合金電極。[Claim 1] Adding 0.01 to 20 w of at least one of iron, iron alloys, or iron compounds to the hydrogen storage alloy.
Hydrogen storage alloy electrode mixed with t%.
、塩である請求項1記載の水素吸蔵合金電極。2. The hydrogen storage alloy electrode according to claim 1, wherein the iron compound is an oxide, hydroxide, or salt of iron.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3032222A JPH04245165A (en) | 1991-01-31 | 1991-01-31 | Hydrogen absorbing alloy electrode |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3032222A JPH04245165A (en) | 1991-01-31 | 1991-01-31 | Hydrogen absorbing alloy electrode |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04245165A true JPH04245165A (en) | 1992-09-01 |
Family
ID=12352925
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3032222A Pending JPH04245165A (en) | 1991-01-31 | 1991-01-31 | Hydrogen absorbing alloy electrode |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04245165A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6444361B1 (en) | 1999-06-14 | 2002-09-03 | Matsushita Electric Industrial Co., Ltd. | Active material for hydrogen storage alloy electrode and method for producing the same |
-
1991
- 1991-01-31 JP JP3032222A patent/JPH04245165A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6444361B1 (en) | 1999-06-14 | 2002-09-03 | Matsushita Electric Industrial Co., Ltd. | Active material for hydrogen storage alloy electrode and method for producing the same |
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