JPH0482162A - Manufacture of electrode made of hydrogen occluding - Google Patents
Manufacture of electrode made of hydrogen occludingInfo
- Publication number
- JPH0482162A JPH0482162A JP2196581A JP19658190A JPH0482162A JP H0482162 A JPH0482162 A JP H0482162A JP 2196581 A JP2196581 A JP 2196581A JP 19658190 A JP19658190 A JP 19658190A JP H0482162 A JPH0482162 A JP H0482162A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- weight
- hydrogen occluding
- hydrogen
- 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.)
- Granted
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 39
- 239000000956 alloy Substances 0.000 claims abstract description 39
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 239000012298 atmosphere Substances 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001122 Mischmetal Inorganic materials 0.000 abstract 1
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 238000004080 punching Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000000126 substance 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
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、金属−水素アルカリ蓄電池等の＊極として用
いられる水素吸蔵合金電極の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for manufacturing a hydrogen storage alloy electrode used as an electrode of a metal-hydrogen alkaline storage battery or the like.
（ロ）従来の技術
従来から用いられている蓄電池としては、ニッケルーカ
ドミウム蓄電池の様なアルカリ蓄電池、あるいは鉛蓄電
池などがあるが、近年、これらの電池よりも軽にかつ高
容量で高エネルギー密度になる可能性のある、水素吸蔵
合金を＊極に用いた金属−水素アルカリ蓄電池が注目さ
れている。(b) Conventional technology Traditionally used storage batteries include alkaline storage batteries such as nickel-cadmium storage batteries, and lead storage batteries, but in recent years, batteries that are lighter, have higher capacity, and have higher energy density than these batteries have been developed. Metal-hydrogen alkaline storage batteries using hydrogen-absorbing alloys as electrodes are attracting attention as they have the potential to become
この種、金属−水素アルカリ蓄電池の負極に用いられる
水素吸蔵合金電極の製造方法としては、水素吸蔵合金粉
末と導電材粉末との混合物を、耐アルカリ電解液性の粒
子状結着剤によって電極支持体に固着させて、水素吸蔵
合金電極とする方法（特公昭５７−３０２７３号公報）
がある。As a method for producing this type of hydrogen storage alloy electrode used as the negative electrode of metal-hydrogen alkaline storage batteries, a mixture of hydrogen storage alloy powder and conductive material powder is supported by a particulate binder that is resistant to alkaline electrolyte. A method of making a hydrogen storage alloy electrode by fixing it on the body (Japanese Patent Publication No. 30273/1983)
There is.
（ハ）発明が解決しようとする課題
しかしながら、上記方法により製造された水素吸蔵合金
電極は、初期容量が低いという欠点があった。これはか
かる電極の製造過程において、水素吸蔵合金の表面が酸
化物に覆われ合金の活性が悪くなるからである。従って
、電池としての安定した高い容量を得るために、化成処
理として数サイクルの充放電が従来必要であった。(c) Problems to be Solved by the Invention However, the hydrogen storage alloy electrode manufactured by the above method had a drawback of having a low initial capacity. This is because during the manufacturing process of such electrodes, the surface of the hydrogen storage alloy is covered with oxides, which deteriorates the activity of the alloy. Therefore, in order to obtain a stable and high capacity as a battery, several cycles of charging and discharging were conventionally required as a chemical conversion treatment.
本発明はかかる従来技術の問題点に鑑み、初期容量を高
め、サイクル特性の良好な電極を製造する方法を提供す
ることを目的とする。In view of the problems of the prior art, it is an object of the present invention to provide a method for manufacturing an electrode with increased initial capacity and good cycle characteristics.
（ニ）課題を解決するための手段
１′、５ピ「１的のため、本発明では、水素吸蔵合金と
炭素材料とを混合し、水素吸蔵合金の融点以下の温度で
焼結することにより水素吸蔵合金電極を製造する。(D) Means for Solving the Problems 1', 5: 'For the purpose of 1, in the present invention, a hydrogen storage alloy and a carbon material are mixed and sintered at a temperature below the melting point of the hydrogen storage alloy. Manufacture hydrogen storage alloy electrodes.
この時混合する炭素材料は水素吸蔵合金の重量に対して
、０．１重量％以上１０．０重量％以下が望ましい。The carbon material mixed at this time is desirably 0.1% by weight or more and 10.0% by weight or less based on the weight of the hydrogen storage alloy.
（ホ）作用
水素吸蔵合金と炭素材料を混合し焼結することにより水
素吸蔵合金粒子表面の酸化物は炭素材料により還元され
水素吸蔵合金は活性化する。従って、この水素吸蔵合金
電極を負極に用いたニッケルー水素アルカリ蓄電池は活
性が高く初期容量の高いものとなる。(E) Function By mixing the hydrogen storage alloy and the carbon material and sintering the mixture, the oxides on the surface of the hydrogen storage alloy particles are reduced by the carbon material and the hydrogen storage alloy is activated. Therefore, a nickel-hydrogen alkaline storage battery using this hydrogen storage alloy electrode as a negative electrode has high activity and a high initial capacity.
さらに、還元反応に使用されなかった炭素材料は導電剤
として働くことにより、水素吸蔵合金粒子間の接触抵抗
が減少する。その結果、前記負極の充放電効率が高くな
り初期容量が高くなると共に、該負極でのガス発生が抑
えられるために電解液の漏液等を防１１．することがで
きるので、前記電池のサイクル特性も向−トする。Furthermore, the carbon material not used in the reduction reaction acts as a conductive agent, thereby reducing the contact resistance between the hydrogen storage alloy particles. As a result, the charging/discharging efficiency of the negative electrode is increased, the initial capacity is increased, and gas generation at the negative electrode is suppressed, thereby preventing electrolyte leakage, etc. 11. Therefore, the cycle characteristics of the battery are also improved.
（へ）実施例
市販のミツシュメタルＭｍ （ランタン１．ａ、セリウ
ムＣｃ、ネオジムＮｄ、プロセオジムＰｒ等の希土類元
素の混合物）、ニッケルＮ１．コバルｈＣｏ、及びアル
ミニウム八１を用い、元素比でＭｍ：Ｎｉ：Ｃｏ：Ａｔ
が］：３：１．５二〇、５となるように秤量して混合し
た。次に、この混合物をアルゴン不活性雰囲気のアーク
炉にて溶解し、ＭｍＮｉ、Ｃｏ、、 ｓＡＩ。５で表さ
れる水素吸蔵合金（融点略１３５０℃）を作製した。こ
の水素吸蔵合金を平均粒径５０μｍになるように機械的
に粉砕した。(f) Examples Commercially available Mitshu Metal Mm (a mixture of rare earth elements such as lanthanum 1.a, cerium Cc, neodymium Nd, and proseodymium Pr), nickel N1. Using cobal hCo and aluminum 81, the elemental ratio is Mm:Ni:Co:At
]:3:1.520.5 and mixed. Next, this mixture was melted in an arc furnace under an argon inert atmosphere to form MmNi, Co, and sAI. A hydrogen storage alloy represented by No. 5 (melting point: approximately 1350°C) was prepared. This hydrogen storage alloy was mechanically pulverized to an average particle size of 50 μm.
この水素吸蔵合金に対して、平均粒径５０μｍからなる
炭素を０．１．０．５．１．０．２．０．３．０．５．
０．１０．０重量２添加し、均一に混合した。これらの
混合物に結着剤としてＩ）ＴＦＥ（フッ素樹脂）粉末５
．０重駄χを添加し、均一に混合することによりＩ）
ＴＩ” ｒｉをＩｉ＆Ｍｔ化し、これに水を加えてペー
スト状とした。このペーストを、ニッケルメッキを施し
たパンチングメタル集主体の両面に圧着し、室温で乾燥
させた。この電極をアルゴンガス雰囲気中、１２００℃
で１０時間焼結した。For this hydrogen storage alloy, 0.1.0.5.1.0.2.0.3.0.5.
0.10.0 weight 2 was added and mixed uniformly. I) TFE (fluororesin) powder 5 as a binder to these mixtures
．． I) by adding 0 heavy weight χ and mixing uniformly
TI"ri was converted into Ii & Mt, and water was added to make a paste. This paste was pressed onto both sides of a nickel-plated punched metal aggregate and dried at room temperature. This electrode was placed in an argon gas atmosphere. , 1200℃
It was sintered for 10 hours.
この様にして作製した負極と、公知の容量１００〇八り
の焼結式ニッケル正極を、耐アルカリ性のセパレータと
共に持回して、渦巻電極体を得、電池外装計にこの電極
体を挿入した。The negative electrode thus produced and a known sintered nickel positive electrode with a capacity of 10008 were carried around together with an alkali-resistant separator to obtain a spiral electrode body, and this electrode body was inserted into a battery case.
また、水素吸蔵合金粉末をこれら正負極と絶縁性を保た
れるようにセパレータで包み、電極体巻心に挿入した。Further, the hydrogen storage alloy powder was wrapped with a separator so as to maintain insulation from these positive and negative electrodes, and inserted into the electrode core.
この後、電解液を注液し、封口を行い、本発明による円
筒密閉型ニッケル水素アルカリ蓄電池ＡＩ−Ａ７を作製
した。ここで電池Ａ１は炭素が０．１重量％、八２が０
．５重量％、Ａ３が１．０重量％、Ａ４カ２ 、０重量
Ｚ、 Ａ５カ３．０重量２、八６が５．０重量％、 Ａ
７カ１０．０重量２である。Thereafter, an electrolytic solution was injected and the container was sealed to produce a sealed cylindrical nickel-hydrogen alkaline storage battery AI-A7 according to the present invention. Here, in battery A1, carbon is 0.1% by weight and 82 is 0.
．． 5 weight%, A3 1.0 weight%, A4 size 2, 0 weight Z, A5 size 3.0 weight 2, 86 5.0 weight%, A
The weight is 7, 10.0, and 2.
また比較例として、炭素を添加せずに水素吸蔵合金にＩ
） Ｔ Ｆ Ｅ ５重量％を混合し、前記の方法と同様
にして作製された負極を備えた比較電池＾８を得た。In addition, as a comparative example, I was added to a hydrogen storage alloy without adding carbon.
) 5% by weight of TFE was mixed to obtain a comparative battery^8 equipped with a negative electrode prepared in the same manner as the above method.
この様にして得られた本発明電池層〜航、及び比較電池
Ａ８を用い、ＩＡの電流で、１．２時間充電した後、Ｉ
Ａの電流で電池電圧が１，０■になるまで放電を行い、
初期容量及び放電容量が半減するまでのサイクル寿命を
調べた。Using the battery layers of the present invention obtained in this way and the comparative battery A8, after charging at a current of IA for 1.2 hours,
Discharge the battery with a current of A until the battery voltage reaches 1.0■,
The cycle life until the initial capacity and discharge capacity were reduced by half was investigated.
これらの結果を夫々第１図、及び第２図に示す。この結
果より、炭素の添加量が増加するほど初期容量は大きく
なり、例えば１．０重量２で略１００１００Ｏになって
いる。この時、正極の容量が１０００ｍΔｈであるので
、この値以上には」ニゲしない。これは水素吸蔵合金粒
子表面の酸化物が炭素により還元され、水素吸蔵合金の
活性が高くなったためである。そして炭素の添加量が１
０．０重量２を越えると、比較電池の初期容量よりも小
さくなってしまうので、０．］〜］０．０重量２の添加
量が望ましいと言える。These results are shown in FIGS. 1 and 2, respectively. From this result, as the amount of carbon added increases, the initial capacity increases, for example, approximately 100,100 O at 1.0 weight 2. At this time, since the capacity of the positive electrode is 1000 mΔh, it will not swell beyond this value. This is because the oxide on the surface of the hydrogen storage alloy particles was reduced by carbon, and the activity of the hydrogen storage alloy became high. And the amount of carbon added is 1
If it exceeds 0.0 weight 2, the initial capacity will be smaller than the comparison battery, so 0.0 weight 2 will be exceeded. ]~]0.0wt2 is preferable.
また、酸化物の還元に使用された炭素が水素吸蔵合金か
ら抜は出た後は、その部位が空間となり、電極は多孔質
に成る。このため、電極内部まで電解液が浸透し、負極
の初期活性が高くなると考えられる。Further, after the carbon used to reduce the oxide is extracted from the hydrogen storage alloy, the space becomes a space, and the electrode becomes porous. For this reason, it is thought that the electrolytic solution permeates into the inside of the electrode, increasing the initial activity of the negative electrode.
さらに、還元反応に使用されずに残留した炭素は導電剤
として働き、負極の充放電効率が高くなるために初期容
量は大きくなると考えられる。Furthermore, it is thought that the carbon remaining without being used in the reduction reaction acts as a conductive agent, increasing the charging/discharging efficiency of the negative electrode and increasing the initial capacity.
方、サイクル寿命は炭素の添加率１．０重量％の場合に
８ （１０回で、無添加の場合の４００回の約２倍にな
っている。そして炭素の添加量が２０重量２より多くな
るとサイクル寿命が減少してくるが、これは負極の合金
量が減少するためである。On the other hand, when the carbon addition rate is 1.0% by weight, the cycle life is 8 (10 cycles, which is about twice the 400 cycles without additives. In this case, the cycle life decreases, but this is because the amount of alloy in the negative electrode decreases.
尚、合金に混合する炭素材料としては黒鉛、カーボンブ
ラック、アセチレンブラック、活性炭など炭素を成分と
する材料であれば同様の効果が期待できる。Note that similar effects can be expected if the carbon material to be mixed into the alloy contains carbon as a component, such as graphite, carbon black, acetylene black, and activated carbon.
（ト）発明の効果
本発明による水素吸蔵合金を負極に用いたニッケルー水
素アルカリ蓄電池は、初期特性及びサイクル特性に優れ
たものとなり、その工業的価値は極めて大きい。(g) Effects of the Invention A nickel-hydrogen alkaline storage battery using the hydrogen storage alloy according to the present invention as a negative electrode has excellent initial characteristics and cycle characteristics, and its industrial value is extremely large.
また、負極でのガス発生が押さえられるために電解液の
漏液を防止できる効果がある。Furthermore, since gas generation at the negative electrode is suppressed, leakage of the electrolytic solution can be prevented.
第１図は初期の電池容量と水素吸蔵合金に対する炭素の
添加量との関係、第２図はサイクル寿命と水素吸蔵合金
に対する炭素の添加量との関係を示す図である。FIG. 1 is a diagram showing the relationship between the initial battery capacity and the amount of carbon added to the hydrogen storage alloy, and FIG. 2 is a diagram showing the relationship between the cycle life and the amount of carbon added to the hydrogen storage alloy.
Claims (2)
を前記水素吸蔵合金の融点以下の温度で焼結することを
特徴とする水素吸蔵合金電極の製造方法。(1) A method for producing a hydrogen storage alloy electrode, which comprises mixing a hydrogen storage alloy and a carbon material, and sintering the mixture at a temperature below the melting point of the hydrogen storage alloy.
に対して０．１重量％以上１０．０重量％以下であるこ
とを特徴とする請求項（１）の水素吸蔵合金電極の製造
方法。(2) Manufacturing the hydrogen storage alloy electrode according to claim (1), wherein the amount of the carbon material added is 0.1% by weight or more and 10.0% by weight or less based on the weight of the hydrogen storage alloy. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2196581A JP2994704B2 (en) | 1990-07-24 | 1990-07-24 | Manufacturing method of hydrogen storage alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2196581A JP2994704B2 (en) | 1990-07-24 | 1990-07-24 | Manufacturing method of hydrogen storage alloy electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0482162A true JPH0482162A (en) | 1992-03-16 |
| JP2994704B2 JP2994704B2 (en) | 1999-12-27 |
Family
ID=16360124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2196581A Expired - Fee Related JP2994704B2 (en) | 1990-07-24 | 1990-07-24 | Manufacturing method of hydrogen storage alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2994704B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287725B1 (en) * | 1997-04-02 | 2001-09-11 | Sanyo Electric Co., Ltd. | Sintered hydrogen storage alloy electrode and nickel-hydrogen storage battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5730273B2 (en) | 2012-11-26 | 2015-06-03 | 株式会社日本製鋼所 | Electromagnetic accelerator |
-
1990
- 1990-07-24 JP JP2196581A patent/JP2994704B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287725B1 (en) * | 1997-04-02 | 2001-09-11 | Sanyo Electric Co., Ltd. | Sintered hydrogen storage alloy electrode and nickel-hydrogen storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2994704B2 (en) | 1999-12-27 |
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