JPH04190959A - Manufacture of hydrogen occluding alloy - Google Patents
Manufacture of hydrogen occluding alloyInfo
- Publication number
- JPH04190959A JPH04190959A JP2316216A JP31621690A JPH04190959A JP H04190959 A JPH04190959 A JP H04190959A JP 2316216 A JP2316216 A JP 2316216A JP 31621690 A JP31621690 A JP 31621690A JP H04190959 A JPH04190959 A JP H04190959A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- metal
- contact
- segregation
- vacuum
- 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 15
- 239000000956 alloy Substances 0.000 title claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 title claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000003860 storage Methods 0.000 claims description 6
- 238000005204 segregation Methods 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw 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
【発明の詳細な説明】
、巖１ユ１１す１年団
本発明は金属組織上結晶粒の形状と大きさが比較的均一
で、ミクロ偏析の弱い希土類元素およびニッケル等を主
成分とする２次電池用のＭｍ Ｎｉ １−Ｘ−Ｙ−Ｚ
ＭｎｘＡｌｙＣｏｚ （Ｍｍ ：ミッシュメタル）等の
水素吸蔵合金の製造方法に関するものである。[Detailed description of the invention] The present invention is based on a metallographic structure in which the shape and size of crystal grains are relatively uniform, and the main components are rare earth elements and nickel, which have weak micro-segregation. Mm Ni 1-X-Y-Z for next battery
The present invention relates to a method for manufacturing hydrogen storage alloys such as MnxAlyCoz (Mm: misch metal).
夫米Ω弦皿
従来希土類元素およびニッケルを主成分とし、マンカン
、アルミニウム、コバルト等を含む水素吸蔵合金は溶解
後、円筒状のインコツトに鋳造し粗粉砕、熱処理、微粉
砕等の工程を経て、２次電池の負極材料用として用いら
れてきた。しかしながら、インゴットの結晶粒が柱状晶
と等軸晶の混在する状況であり、かつ結晶粒の太きさも
不均一であった。さらに、希土類元素、マンガン等の顕
著なミクロ偏析が認められ結晶粒の不均一と合わせて、
２次電池用途においてきられれる特性のばらつきと再現
性の無さの原因となっている。Fubei Omega String Dish Conventionally, a hydrogen storage alloy whose main components are rare earth elements and nickel, and which also contains mankan, aluminum, cobalt, etc., is melted and then cast into a cylindrical inkotsuto, which undergoes processes such as coarse pulverization, heat treatment, and fine pulverization. It has been used as a negative electrode material for secondary batteries. However, the crystal grains of the ingot were a mixture of columnar crystals and equiaxed crystals, and the thickness of the crystal grains was also non-uniform. Furthermore, remarkable micro-segregation of rare earth elements, manganese, etc. was observed, and together with the non-uniformity of crystal grains,
This causes variations in characteristics and lack of reproducibility in secondary battery applications.
ｌが解むしようとする間町点
本発明はかかる不具合を除去したもので、水素吸蔵合金
インゴットの金属組織における結晶粒の不均一性とミク
ロ偏析についてそれらを解消し、２次電池用に用いる場
合、特性のばらつきのないこと及び再現性あるものを製
造することを目的とする。The present invention eliminates such problems, and eliminates the unevenness and microsegregation of crystal grains in the metal structure of hydrogen storage alloy ingots, which are used for secondary batteries. In this case, the aim is to manufacture products with consistent characteristics and reproducibility.
副題点を１、するための手段 ひ作
発明者は、上記問題点を解決すべく鋭意研究した結果以
下の発明をなした。Means for achieving subtitle 1. The inventor Hisaku made the following invention as a result of intensive research to solve the above problems.
即ち本発明は、合金溶解後、片面が金属製鋳型と接する
ように厚さ７〜４０鵬の板状に鋳造するか、両面が金属
製鋳型と接するように厚さ１４〜８０ＩｎＩＴｌの板状
に真空中あるいは不活性ガス中で鋳造後、１０００〜１
２００℃で真空中あるいは不活性カス中で熱処理するこ
とを特徴とする水素吸蔵合金の製造方法に関する。That is, in the present invention, after the alloy is melted, it is cast into a plate shape with a thickness of 7 to 40 InITl so that one side is in contact with a metal mold, or it is cast into a plate shape with a thickness of 14 to 80 InITl so that both sides are in contact with a metal mold. 1000-1 after casting in vacuum or inert gas
The present invention relates to a method for producing a hydrogen storage alloy, which is characterized by heat treatment at 200° C. in vacuum or in an inert scum.
以下本発明について詳細に説明する。The present invention will be explained in detail below.
原料は市販のミツシュメタル、電解ニッケル（３Ｎ〜４
Ｎ）、電解コバルト（３Ｎ）、フレーク状マンガン（３
Ｎ）、アルミニウムショット（３Ｎ）を使用すればよい
。The raw materials are commercially available Mitshu metal, electrolytic nickel (3N to 4
N), electrolytic cobalt (3N), flaky manganese (3N), electrolytic cobalt (3N), manganese flake (3N),
N), aluminum shot (3N) may be used.
溶解は１３３０−１３８０℃でカルシするつぼを使用し
高周波誘導溶解炉にて行う。溶解の雰囲気は不活性ガス
もしくはＩ Ｘ １０３〜Ｉ Ｘ １０−’Ｔｏｒｒの
真空とする。まずニッケルおよびコバルトとミツシュメ
タルを溶解して、マンガンおよびアルミニウムを添加す
る。その後２〜１５分間保持してインゴット２〜４０ｋ
ｇに鋳造する。Melting is carried out in a high-frequency induction melting furnace using a calcining crucible at 1330-1380°C. The atmosphere for dissolution is an inert gas or a vacuum of I x 103 to I x 10 -' Torr. First, nickel and cobalt and Mitsushmetal are melted and manganese and aluminum are added. After that, hold for 2-15 minutes and make an ingot of 2-40k.
Cast to g.
鋳造においては、結晶粒の均一性とミクロ偏析の解消と
いった観点から第１図に示すごとく溶解温度から１００
０℃までの平均冷却速度で３．５℃／ｓｅｃ以上が好ま
しい。次工程での熱処理による偏析除去に極めて好まし
い結果を与えるからである。このような条件を満たすべ
く鋳型は冷却の速い金属製鋳型を用いる。材質としては
鋳鉄、水冷銅鋳型等でよい。さらに冷却を早めるべくイ
ンゴットは板形状とする。板面を水平とし、底部が板面
と接するようにした場合厚みは７〜４０Ｍとする。４０
ｍｍ以上では目的とする結晶粒の均一性とミクロ偏析の
解消を達成できず、７Ｍ以下とすると鋳造が困難であり
、さらには、広い面積を要して好ましくない。また冷却
速度の観点から明らかに板面を垂直にし、両面が鋳型と
接するようにした場合１４〜８０ｍｍにて同等の効果を
得る。In casting, from the viewpoint of uniformity of crystal grains and elimination of micro-segregation, the melting temperature is lowered by 100% as shown in Figure 1.
The average cooling rate to 0°C is preferably 3.5°C/sec or more. This is because it provides extremely favorable results for removing segregation by heat treatment in the next step. In order to meet these conditions, a metal mold that cools quickly is used. The material may be cast iron, water-cooled copper mold, etc. In order to further speed up cooling, the ingot is shaped into a plate. When the plate surface is horizontal and the bottom is in contact with the plate surface, the thickness is 7 to 40M. 40
If it is more than 7 mm, it will not be possible to achieve the desired uniformity of crystal grains and eliminate micro-segregation, and if it is less than 7 M, it will be difficult to cast, and furthermore, it will require a large area, which is not preferable. Moreover, from the viewpoint of cooling rate, if the plate surface is made vertical and both surfaces are in contact with the mold, the same effect can be obtained at 14 to 80 mm.
このようにして作製したインゴットは５〜１０印に粗粉
砕して１０００〜１２００℃にて２〜１０時間行う。こ
れは、ミクロ偏析をなくすため好適な範凹だからである
。不活性ガス又は１０−’Ｔｏｒｒ程度の真空雰囲気に
て熱処理を行う。特に冷却速度の速いインゴットは水素
吸収放出における圧力−濃度−温度曲線において濃度の
変化に対し圧力の変化が少ないいわゆるプラトー領域を
示さないが、熱処理によりプラトー領域が認められるよ
うになる。The ingot thus produced is coarsely pulverized into 5 to 10 marks and subjected to heating at 1000 to 1200°C for 2 to 10 hours. This is because the range is suitable for eliminating micro-segregation. Heat treatment is performed in an inert gas or vacuum atmosphere of about 10-' Torr. Particularly, ingots with a fast cooling rate do not exhibit a so-called plateau region in the pressure-concentration-temperature curve during hydrogen absorption and desorption, in which the pressure changes little with respect to concentration changes, but the plateau region becomes visible after heat treatment.
上記熱処理の後、０．５ｍｍ以下に微粉砕して２次電池
用負極材料に用いる。After the above heat treatment, it is finely pulverized to 0.5 mm or less and used as a negative electrode material for secondary batteries.
失］Ｌ久
市販のミツシュメタル、電解ニッケル（３Ｎ）、電解コ
バルト（３Ｎ）、フレーク状マンガン（３Ｎ）、アルミ
ニウムショット（３Ｎ）を使用してＭ ｍ Ｎ ｉ、、
、Ｍｎ、、、Ａ １．、、Ｃｏ６．、の組成のインゴッ
トを真空中１３３０℃で８〜５４ｍｍの厚みの板に鋳造
した。M m N i, using commercially available Mitsushi metal, electrolytic nickel (3N), electrolytic cobalt (3N), flaky manganese (3N), and aluminum shot (3N).
,Mn,,,A 1. ,,Co6. An ingot having a composition of , was cast in vacuum at 1330° C. into a plate having a thickness of 8 to 54 mm.
鋳造したインゴット約２ｋｇおよびインゴットを５〜１
０ｍｍに粗粉砕して１１００℃×５時間の熱処理をほど
こした材料について光学顕微鏡にて結晶粒の観察を行い
、さらにＸ線マイクロアナライザーにてミクロ偏析の調
査を行った。その結果、以下の表のＮｏ、 １〜６のご
とく好ましい結果を得た。さらにＮｏ、 ７〜１０を比
較の為同様に調べた結果本発明の実施例が優れている事
を確認した。Approximately 2 kg of cast ingots and 5 to 1 ingots
The material was coarsely ground to 0 mm and heat treated at 1100° C. for 5 hours, and the crystal grains were observed using an optical microscope, and microsegregation was investigated using an X-ray microanalyzer. As a result, favorable results were obtained as shown in Nos. 1 to 6 in the table below. Furthermore, as a result of similarly examining Nos. 7 to 10 for comparison, it was confirmed that the examples of the present invention were superior.
即ち、片面が鋳型と接する場合、４０ｍｍ以下の厚みで
結晶粒が均一であり、ミクロ偏析か弱く、かつ熱処理で
ミクロ偏析の解消が認められるのに対し、４０ｍｍより
大きい板厚では結晶粒が不均一かつミクロ偏析が残る。In other words, when one side is in contact with the mold, the crystal grains are uniform with a thickness of 40 mm or less and the micro-segregation is weak, and the micro-segregation can be resolved by heat treatment, whereas the crystal grains are non-uniform with a thickness greater than 40 mm. And micro-segregation remains.
ミクロ偏析はインゴットではＭｎ、Ｌａ、ＣＩについて
著しく、熱処理材ではいずれもＭｎのミクロ偏析は解消
されていたが、Ｌａ、Ｃ１については残っていた。In the ingot, the micro-segregation was remarkable for Mn, La, and CI, and in the heat-treated material, the micro-segregation of Mn was eliminated, but it remained for La and C1.
両面が鋳型と接する場合についても８０ｍｍ以下の厚み
で、結晶粒が均一で、ミクロ偏析か弱く、かつ熱処理で
ミクロ偏析の解消が認められた。Even when both sides were in contact with the mold, the thickness was 80 mm or less, the crystal grains were uniform, the micro-segregation was weak, and it was observed that the micro-segregation was eliminated by heat treatment.
さらに実施例および比較例について、電池容量およびサ
イクル寿命のばらつきを調査した所、実施例のばらつき
は比較例より小さく、再現性に優れていた。Further, when the variations in battery capacity and cycle life were investigated for the Examples and Comparative Examples, the variations in the Examples were smaller than in the Comparative Examples, and the reproducibility was excellent.
以下余白
以上説明したように、水素吸蔵合金を溶解後片面が金属
製鋳型と接するように厚さ７〜４０ｍｍの板状に鋳造す
るか両面が金属製鋳型と接するように厚さ１４〜８０ｉ
１１Ｔｌの板状に鋳造する事には結晶粒が均一でミクロ
偏析の弱い材料を提供する事ができ、その同一の合金を
使用したそれぞれの２次電池特性のばらつきと再現性の
なさを解消する。As explained above, after melting the hydrogen storage alloy, it is cast into a plate shape with a thickness of 7 to 40 mm so that one side is in contact with the metal mold, or a plate with a thickness of 14 to 80 mm so that both sides are in contact with the metal mold.
Casting 11Tl into a plate shape can provide a material with uniform crystal grains and weak micro-segregation, which eliminates the variation and lack of reproducibility in the characteristics of secondary batteries using the same alloy. .
第１図、本発明における鋳型インゴットの厚みと冷却速
度を示す。FIG. 1 shows the thickness and cooling rate of the mold ingot in the present invention.
Claims (1)
さ７〜４０ｍｍの板状に鋳造するか、両面が金属製鋳型
と接するように厚さ１４〜８０ｍｍの板状に真空中ある
いは不活性ガス中で鋳造後、１０００〜１２００℃で真
空中あるいは不活性ガス中で熱処理することを特徴とす
る水素吸蔵合金の製造方法。(1) After the alloy is melted, it is cast into a plate with a thickness of 7 to 40 mm so that one side is in contact with a metal mold, or cast into a plate with a thickness of 14 to 80 mm so that both sides are in contact with a metal mold in a vacuum or A method for producing a hydrogen storage alloy, which comprises casting in an inert gas and then heat-treating the alloy at 1000 to 1200°C in a vacuum or in an inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2316216A JPH04190959A (en) | 1990-11-22 | 1990-11-22 | Manufacture of hydrogen occluding alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2316216A JPH04190959A (en) | 1990-11-22 | 1990-11-22 | Manufacture of hydrogen occluding alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04190959A true JPH04190959A (en) | 1992-07-09 |
Family
ID=18074597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2316216A Pending JPH04190959A (en) | 1990-11-22 | 1990-11-22 | Manufacture of hydrogen occluding alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04190959A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5817222A (en) * | 1995-04-03 | 1998-10-06 | Santoku Metal Industry Co., Ltd. | Rare earth metal-nickel hydrogen storage alloy, process for producing the same, and anode for nickel-hydrogen rechargeable battery |
| JP2002212601A (en) * | 2001-01-15 | 2002-07-31 | Mitsui Mining & Smelting Co Ltd | Method for producing hydrogen occlusion alloy |
| JP2022020892A (en) * | 2020-07-21 | 2022-02-02 | 新日本電工株式会社 | HYDROGEN STORAGE ALLOY POWDER OF LOW Co CONTENT |
-
1990
- 1990-11-22 JP JP2316216A patent/JPH04190959A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5817222A (en) * | 1995-04-03 | 1998-10-06 | Santoku Metal Industry Co., Ltd. | Rare earth metal-nickel hydrogen storage alloy, process for producing the same, and anode for nickel-hydrogen rechargeable battery |
| JP2002212601A (en) * | 2001-01-15 | 2002-07-31 | Mitsui Mining & Smelting Co Ltd | Method for producing hydrogen occlusion alloy |
| JP2022020892A (en) * | 2020-07-21 | 2022-02-02 | 新日本電工株式会社 | HYDROGEN STORAGE ALLOY POWDER OF LOW Co CONTENT |
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