JPH0321615B2 - - Google Patents

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Publication number
JPH0321615B2
JPH0321615B2 JP59088058A JP8805884A JPH0321615B2 JP H0321615 B2 JPH0321615 B2 JP H0321615B2 JP 59088058 A JP59088058 A JP 59088058A JP 8805884 A JP8805884 A JP 8805884A JP H0321615 B2 JPH0321615 B2 JP H0321615B2
Authority
JP
Japan
Prior art keywords
hydrogen storage
storage material
lmni
metals
mmni
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.)
Expired - Lifetime
Application number
JP59088058A
Other languages
Japanese (ja)
Other versions
JPS60230950A (en
Inventor
Koji Sasai
Noboru Hayamizu
Susumu Uotani
Koichi Oku
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Metals and Chemical Co Ltd
Original Assignee
Japan Metals and Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Metals and Chemical Co Ltd filed Critical Japan Metals and Chemical Co Ltd
Priority to JP59088058A priority Critical patent/JPS60230950A/en
Publication of JPS60230950A publication Critical patent/JPS60230950A/en
Publication of JPH0321615B2 publication Critical patent/JPH0321615B2/ja
Granted legal-status Critical Current

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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
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Landscapes

  • Hydrogen, Water And Hydrids (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

［産業上の利用分野］ 本発明はヒートポンプ等のエネルギー変換又は
温度センサーに利用する交換効率又は感度の優れ
た水素貯蔵材料、特にLm−Ni系の水素貯蔵材料
に関するものである。 ［従来の技術］ 従来、水素貯蔵材料としてTi−Fe系合金、La
−Ni5又はMmNi5（Mmはミツシユメタル）系合
金又はMg系合金からなる各種の材料が提案され
ている。 而して、水素貯蔵用材料に要求される性質とし
て、 (1) 活性化が容易であること、 (2) 水素貯蔵量が大きいこと、 (3) 吸蔵水素圧力と解離平衡圧力との差であるヒ
ステリシスが小さいこと、 (4) プラトーの平坦性 等があり、更にこれらの材料が資源的に豊富であ
つて低廉であることが要求されている。 しかし、LaNi5又はMmNi系合金からなる材料
では、前者は水素貯蔵量が大きく、吸蔵放出速度
が比較的早いという利点がある反面、原料のLa
は高価であり、実用上経済性で問題がある。 これに対し、後者はLaの経済性を改善すべく
開発されたものであるが、一般にMmはCe40〜
50％、La25〜35％その他Nd、Pr、Sm、Gd等の
各種金属からなるものであつて、MmNi5は室温
で活性化するのに100Kg／cm2以上の高圧力水素を
必要とし、またヒステリシスが大きく、実用化が
困難であるという欠点がある。 これを解決するためにMmNi系合金からなる
材料にAl等の第３元素その他の第４元素等を点
火して常温における吸蔵、放出圧力を従来より低
くし、またヒステリシスを小さくするものも提案
されているが（特開昭54−64014号公報）、第３元
素、第４元素を添加することによつて水素吸蔵量
が小さくなるという欠点がある。 この問題を解決するために、本出願人は、先に
希土類金属を含有する水素貯蔵材料の特性を減殺
することなく、しかも常温における活性化が容易
であり、水素吸蔵量が大きく、しかもヒステリシ
スが小さく吸蔵、放出速度の早く、またプラトー
の平坦性を有する水素貯蔵材料を提案した（特願
昭58−20192号）。 即ち、希土類金属がLa40〜70wt％（以下たん
に％という）、Ce0.1〜20％その他Nd、Pr、Sm等
の金属を含有した希土類金属（以下たんにLmと
いう）とNi及びAlの合金からなる水素貯蔵用材
料である。 ［本発明が解決しようとする課題］ しかし、上記合金は、水素吸蔵量が大きくまた
吸蔵放出速度が比較的早く、かつ吸蔵放出圧力の
低下のために有効である反面、ヒステリシスが尚
大きいという問題がある。 本発明の目的は、常温下で比較的低圧力で水素
貯蔵量が大きく、しかもヒステリシスが小さい水
素貯蔵材料を提供することにある。 ［課題を解決するための手段］ 本出願の第１の発明は、一般式LmNi(X-a)Sna
（ただし、LmはLa40〜70％、Ce0.1〜20％その他
Nd、Pr、Sm等の金属を含有した希土類金属；
Ｘは4.8〜5.5、ａは0.01〜1.0）で表されるSn含有
水素貯蔵材料であり、第２の発明は一般式
LmNi(X-a-b)SnaAb（ただし、LmはLa40〜70％、
Ce0.1〜20％その他Nd、Pr、Sm等の金属を含有
した希土類金属；ＡはAl、Mn、Co又はＶの１
種；Ｘは4.8〜5.5、ａ、ｂは夫々0.01〜1.0）で表
されるSn含有水素貯蔵材料である。 ［作用］ 本発明で使用するLmはLa40〜70％、Ce0.1〜
20％その他Nd、Pr、Sm等の金属からなるもの
であつて、かかるLmは天然に産出し精製された
バストネサイト、モナザイト、粗塩化希土類から
Ceの一部又は殆どを除去することによつて簡単
に得られる。 一例を挙げれば、Ceはバストネサイト精鉱、
モナザイト精鉱等を焙焼し、塩酸抽出を行い濾過
することにより大部分が沈澱分離され、得られた
Ceの少ないLm溶液はNH4OH等によつてLmを
水酸化物として沈澱させ、さらにこれを塩化物、
フツカ物とした後、溶融塩電解することによつて
得られる。 本発明の水素貯蔵材料は、Lm、金属Ni及び粒
状Snとを公知の高周波炉又はタングステン電極
アーク溶解炉等によつてアルゴン等の不活性雰囲
気中で加熱熔融した後、適宜熱処理し、粉砕する
ことによつて簡単に特定発明の水素貯蔵材料を得
ることができ、さらにこれにAl、Mn、Co又はＶ
の１種又は２種を添加して第２の発明の一般式の
水素貯蔵材料も簡単に得ることができる。 本発明におけるSnの添加量は、0.01以下ではヒ
ステリシスを減少させる効果がなく、他方1.0以
上ではSnの添加によつて水素吸蔵量が減少する
ため、0.01〜1.0の範囲とする。 また、特定発明であるLmXNi(X-a)SnaにAl、
Mn、Co又はＶの第４元素又は第４元素と第５元
素等を添加した場合ヒステリシスは改善できる
が、前記Al、Mnその他の第４元素及び第５元素
が0.01以下では吸蔵圧力の改善ができず、また
1.0以上では吸蔵量が減少する。従つて、Ａ元素
は0.01〜1.0の範囲とする。 また、前記一般式(1)、(2)におけるＸが5.5より
大きいか或は4.8より小さい場合には水素吸蔵量
の減少を生ずるほか、水素化物が不安定となり、
水素の吸蔵、放出の繰返しによる材料の劣化が起
り易くなるためＸは4.8〜5.5の範囲とすることが
必要である。 ［実施例］ つぎに本発明の製造例について説明し、その効
果を併せて説明する。 製造例 １ Lmに金属Ni及び粒状Snの所定量をアーク溶解
炉中でアルゴン雰囲気下で加熱溶解してLmNi4.9
Sn0.1とLmNi4.8Sn0.2及びLmNi4.7Sn0.3を夫々精製
し、1050℃、８時間熱処理を行つた後、大気中で
９〜100メツシユに粉砕する。尚、比較のために
LmNi5、LmNi4.9Al0.1及びLmNi4.8Al0.2を前記と
同様に製造した。 比較例 １ Laに金属Ni及び粒状Snを製造例１と同様に処
理してLaNi4.7Sn0.3、LaNi5及びLaNi4.7Al0.3を
夫々製造した。 比較例 ２ Mmに前記製造例１と同様にしてMmNi4.7
Sn0.3、MmNi5及びMmNi4.7Al0.3を製造した。 製造例 ２ Lm及びMmを用い、これに金属Ni、粒状Sn及
び一般式(2)のＡ元素としてMn、Co、Ｖ、Alの１
元素を添加し、前記製造例１と同様に処理して
LmNi4.4Sn0.1Mn0.5、LmNi4.4Sn0.3Co0.3及び比較
のためにMmNi4.65Sn0.3V0.05、MmNi4.6Sn0.2Al0.2
を夫々製造した。 前記で製造した粉砕物を反応容器に封入し、室
温で該容器内を水素ガスで置換し、容器内を30
Kg／cm2の水素圧として活性化する。 つぎに、吸蔵したH2を排気後、30℃における
H2の吸蔵、放出量及びその平衡圧力を測定し、
第１表の如き結果を得た。 [Industrial Application Field] The present invention relates to a hydrogen storage material with excellent exchange efficiency or sensitivity, which is used in energy conversion such as a heat pump or a temperature sensor, and in particular to an Lm-Ni-based hydrogen storage material. [Conventional technology] Conventionally, Ti-Fe alloys and La
- Various materials made of Ni 5 or MmNi 5 (Mm is Mitsushi Metal) based alloys or Mg based alloys have been proposed. Therefore, the properties required for a hydrogen storage material are (1) ease of activation, (2) large hydrogen storage capacity, and (3) the ability to (4) flatness of the plateau, etc., and these materials are also required to be abundant in resources and inexpensive. However, when it comes to materials made of LaNi 5 or MmNi alloys, while the former has the advantage of having a large hydrogen storage capacity and a relatively fast absorption and desorption rate, the raw material La
is expensive and has a practical economical problem. On the other hand, the latter was developed to improve the economic efficiency of La, but generally Mm is Ce40 ~
50% La, 25~35% La, and various other metals such as Nd, Pr, Sm, and Gd. MmNi 5 requires high pressure hydrogen of 100 Kg/cm 2 or more to activate at room temperature, and The drawback is that it has large hysteresis and is difficult to put into practical use. To solve this problem, a method has been proposed in which a third element such as Al or another fourth element is ignited in a material made of MmNi alloy to lower the occlusion and release pressure at room temperature than before and to reduce the hysteresis. However, the addition of the third element and the fourth element has the disadvantage that the amount of hydrogen storage becomes smaller. In order to solve this problem, the applicant has developed a hydrogen storage material containing rare earth metals that can be easily activated at room temperature, has a large hydrogen storage capacity, and has a low hysteresis without first reducing the properties of the hydrogen storage material. We have proposed a hydrogen storage material that is small in size, has a fast absorption and release rate, and has a flat plateau (Japanese Patent Application No. 58-20192). That is, an alloy of rare earth metals (hereinafter simply referred to as Lm), Ni and Al containing 40 to 70 wt% of rare earth metals (hereinafter simply referred to as %) and 0.1 to 20% of Ce and other metals such as Nd, Pr, and Sm. It is a hydrogen storage material consisting of [Problems to be Solved by the Present Invention] However, while the above alloy has a large hydrogen storage capacity, a relatively fast storage and release rate, and is effective for reducing storage and release pressure, it still has a problem of large hysteresis. There is. An object of the present invention is to provide a hydrogen storage material that has a large hydrogen storage capacity at room temperature and relatively low pressure, and has small hysteresis. [Means for solving the problem] The first invention of the present application has the general formula LmNi (Xa) Sn a
(However, Lm is La40~70%, Ce0.1~20%, etc.
Rare earth metals containing metals such as Nd, Pr, and Sm;
X is 4.8 to 5.5, a is 0.01 to 1.0), and the second invention is an Sn-containing hydrogen storage material represented by the general formula
LmNi (Xab) Sn a A b (However, Lm is La40~70%,
Ce0.1~20% Rare earth metal containing other metals such as Nd, Pr, Sm; A is 1 of Al, Mn, Co or V
Species; X is 4.8 to 5.5, and a and b are each 0.01 to 1.0). [Function] Lm used in the present invention is La40~70%, Ce0.1~
20% other metals such as Nd, Pr, and Sm, and such Lm is derived from naturally occurring and purified bastnaesite, monazite, and crude rare earth chlorides.
It can be easily obtained by removing part or most of Ce. For example, Ce is bastnaesite concentrate,
Most of the monazite concentrate was separated by precipitation by roasting, extracting with hydrochloric acid, and filtering.
The Ce-poor Lm solution precipitates Lm as a hydroxide using NH 4 OH, etc., and then converts this into chloride,
It is obtained by making it into a soft substance and then subjecting it to molten salt electrolysis. The hydrogen storage material of the present invention is prepared by heating and melting Lm, metallic Ni, and granular Sn in an inert atmosphere such as argon in a known high frequency furnace or tungsten electrode arc melting furnace, followed by heat treatment as appropriate and pulverization. By this, it is possible to easily obtain the hydrogen storage material of the specified invention, and furthermore, it is possible to easily obtain the hydrogen storage material of the specified invention, and furthermore, it is possible to obtain the hydrogen storage material of the specified invention.
The hydrogen storage material of the general formula of the second invention can also be easily obtained by adding one or two of the following. The amount of Sn added in the present invention is set in the range of 0.01 to 1.0, because if it is less than 0.01, there is no effect of reducing hysteresis, and if it is more than 1.0, the hydrogen storage amount will be reduced by the addition of Sn. In addition, Al, Lm X Ni (Xa) Sn a , which is a specified invention,
Hysteresis can be improved by adding a fourth element such as Mn, Co, or V, or a fourth element and a fifth element, but if the content of the fourth element and fifth element such as Al, Mn, etc. is 0.01 or less, the storage pressure cannot be improved. I can't do it again
Above 1.0, the storage capacity decreases. Therefore, the A element should be in the range of 0.01 to 1.0. Furthermore, if X in the above general formulas (1) and (2) is larger than 5.5 or smaller than 4.8, not only will the hydrogen storage capacity decrease, but the hydride will become unstable.
Since the material tends to deteriorate due to repeated absorption and release of hydrogen, it is necessary that X be in the range of 4.8 to 5.5. [Example] Next, manufacturing examples of the present invention will be explained, and the effects thereof will also be explained. Production example 1 LmNi 4.9 is obtained by heating and melting a predetermined amount of metal Ni and granular Sn in Lm in an argon atmosphere in an arc melting furnace.
Sn 0.1 , LmNi 4.8 Sn 0.2 , and LmNi 4.7 Sn 0.3 are each purified, heat treated at 1050°C for 8 hours, and then ground into 9 to 100 meshes in the air. For comparison,
LmNi 5 , LmNi 4.9 Al 0.1 and LmNi 4.8 Al 0.2 were produced in the same manner as above. Comparative Example 1 La was treated with metallic Ni and granular Sn in the same manner as in Production Example 1 to produce LaNi 4.7 Sn 0.3 , LaNi 5 , and LaNi 4.7 Al 0.3 , respectively. Comparative Example 2 MmNi 4.7 was added to Mm in the same manner as in Production Example 1.
Sn 0.3 , MmNi 5 and MmNi 4.7 Al 0.3 were produced. Production example 2 Using Lm and Mm, metallic Ni, granular Sn, and one of Mn, Co, V, and Al as the A element of general formula (2)
The elements were added and treated in the same manner as in Production Example 1.
LmNi 4.4 Sn 0.1 Mn 0.5 , LmNi 4.4 Sn 0.3 Co 0.3 and for comparison MmNi 4.65 Sn 0.3 V 0.05 , MmNi 4.6 Sn 0.2 Al 0.2
were manufactured respectively. The pulverized product produced above was sealed in a reaction container, and the inside of the container was replaced with hydrogen gas at room temperature.
Activate as hydrogen pressure of Kg/cm 2 . Next, after exhausting the occluded H2 ,
Measure the storage and release amount of H2 and its equilibrium pressure,
The results shown in Table 1 were obtained.

【表】 第１表から明らかな如く、Snを添加した本発
明は、比較例に比べて何れもヒステリシス因子
[Table] As is clear from Table 1, the present invention with Sn added has a lower hysteresis factor than the comparative example.

【In（Pa／Pd）】は大巾に改善されており、また吸
蔵圧力（Pa）、放出圧力（Pd）も著しく改善され
ていることが認められ、しかもH2の最大吸蔵量
[In (Pa/Pd)] has been significantly improved, and it has been recognized that storage pressure (Pa ) and release pressure (Pd) have also been significantly improved.

【（Ｈ／Ｍ）nax】も比較例と遜色のないものである
ことが認められる。 ［効果］ 以上の如く本発明はLm−Ni系合金にSnを添加
することによつてヒステリシスが減少するため、
ヒートポンプ等のエネルギー変化用に利用する場
合変換効率が向上し、また温度センサーに利用し
た場合、その感度を向上し、性能の優れた水素貯
蔵材料を提供することができる。[(H/M) nax ] was also found to be comparable to the comparative example. [Effect] As described above, the present invention reduces hysteresis by adding Sn to the Lm-Ni alloy.
When used for energy change such as a heat pump, the conversion efficiency is improved, and when used as a temperature sensor, the sensitivity is improved, making it possible to provide a hydrogen storage material with excellent performance.

Claims (1)

【特許請求の範囲】 １ 一般式LmNi(X-a)Sn ａ （ただし、LmはLa40〜70wt％、Ce0.1〜20wt％
その他Nd、Pr、Sm等の金属を含有した希土類
金属；Ｘは4.8〜5.5、ａは0.01〜1.0） で表されるSn含有水素貯蔵材料。 ２ 一般式LmNi(X-a-b)Sn ａ Ab （ただし、LmはLa40〜70wt％、Ce0.1〜20wt％
その他Nd、Pr、Sm等の金属を含有した希土類
金属：ＡはAl、Mn、Co又はＶの１種；Ｘは4.8
〜5.5、ａ、ｂは夫々0.01〜1.0） で表されるSn含有水素貯蔵材料。[Claims] 1 General formula LmNi (Xa) Sn a (Lm is La40~70wt%, Ce0.1~20wt%
A rare earth metal containing other metals such as Nd, Pr, and Sm; where X is 4.8 to 5.5 and a is 0.01 to 1.0). 2 General formula LmNi (Xab) Sn a Ab (Lm is La40~70wt%, Ce0.1~20wt%
Rare earth metals containing other metals such as Nd, Pr, and Sm: A is one of Al, Mn, Co, or V; X is 4.8
~5.5, a and b are each 0.01 to 1.0) Sn-containing hydrogen storage material.
JP59088058A 1984-05-01 1984-05-01 Hydrogen storing material Granted JPS60230950A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP59088058A JPS60230950A (en) 1984-05-01 1984-05-01 Hydrogen storing material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59088058A JPS60230950A (en) 1984-05-01 1984-05-01 Hydrogen storing material

Publications (2)

Publication Number Publication Date
JPS60230950A JPS60230950A (en) 1985-11-16
JPH0321615B2 true JPH0321615B2 (en) 1991-03-25

Family

ID=13932239

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59088058A Granted JPS60230950A (en) 1984-05-01 1984-05-01 Hydrogen storing material

Country Status (1)

Country Link
JP (1) JPS60230950A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62287031A (en) * 1986-06-06 1987-12-12 Sumitomo Heavy Ind Ltd Tritium storage and supply material
JPS62294145A (en) * 1986-06-13 1987-12-21 Santoku Kinzoku Kogyo Kk Metallic alloy for hydrogen storage containing rare earth element and nickel
JPS6347345A (en) * 1986-08-14 1988-02-29 Japan Metals & Chem Co Ltd Hydrogen storage material
KR101826620B1 (en) 2010-08-19 2018-02-07 가부시키가이샤 산도쿠 Hydrogen absorbing alloy, negative pole, and nickel-hydrogen secondary battery
CN113881872B (en) * 2021-10-27 2022-05-20 厦门钨业股份有限公司 Low-cobalt high-rate AB5 type hydrogen storage alloy and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58217655A (en) * 1982-06-11 1983-12-17 Agency Of Ind Science & Technol Hydrogen occluding multi-component alloy
JPS59143036A (en) * 1983-02-02 1984-08-16 Agency Of Ind Science & Technol Ternary alloy of rare earth element for occluding hydrogen

Also Published As

Publication number Publication date
JPS60230950A (en) 1985-11-16

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