JPH02220355A - Hydrogen storage alloy electrode - Google Patents
Hydrogen storage alloy electrodeInfo
- Publication number
- JPH02220355A JPH02220355A JP1040894A JP4089489A JPH02220355A JP H02220355 A JPH02220355 A JP H02220355A JP 1040894 A JP1040894 A JP 1040894A JP 4089489 A JP4089489 A JP 4089489A JP H02220355 A JPH02220355 A JP H02220355A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- hydrogen storage
- electrode
- storage alloy
- 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
- 239000000956 alloy Substances 0.000 title claims abstract description 41
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 40
- 239000001257 hydrogen Substances 0.000 title claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000003860 storage Methods 0.000 title claims abstract description 30
- 150000004678 hydrides Chemical class 0.000 claims abstract description 5
- 230000004913 activation Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000008188 pellet Substances 0.000 abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000010314 arc-melting process Methods 0.000 abstract 1
- 239000011362 coarse particle Substances 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000004845 hydriding Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229910002335 LaNi5 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、二次電池などの負極に用いる、電気化学的に
水素の吸蔵・放出が可能な二次電池用の水素吸蔵合金電
極に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a hydrogen storage alloy electrode for secondary batteries that is capable of electrochemically absorbing and desorbing hydrogen, which is used as a negative electrode for secondary batteries and the like. It is.
（従来の技術）
従来二次電池としては、ニッケルーカドミウム蓄電池、
鉛蓄電池等がよく知られているが、これらの蓄電池は単
位重量又は単位体積当たりのエネルギー密度が比較的小
さい欠点がある。そこで電気化学的に多量の水素を吸蔵
・放出が可能な水素吸蔵合金を用いた電極を負極とし、
正極にはニッケル酸化物を用い電解液としてアルカリ水
溶液を用いたエネルギー密度の大きいニッケルー水素電
池が提案されている。ここでの負極にはＬａＮｉ５等の
水素吸蔵合金が用いられている。(Conventional technology) Conventional secondary batteries include nickel-cadmium storage batteries,
Although lead-acid batteries and the like are well known, these batteries have the drawback of relatively low energy density per unit weight or unit volume. Therefore, we used an electrode made of a hydrogen storage alloy that can electrochemically absorb and release a large amount of hydrogen as a negative electrode.
A nickel-hydrogen battery with high energy density has been proposed that uses nickel oxide for the positive electrode and an alkaline aqueous solution as the electrolyte. A hydrogen storage alloy such as LaNi5 is used for the negative electrode here.
（発明が解決しようとする課題）
しかしながら、上記従来の水素吸蔵合金は、常温に於け
る水素解離圧が２気圧以上となり常圧で電気化学的に充
分な水素を吸蔵させることが困難であり実用的とは言え
なかった。(Problems to be Solved by the Invention) However, in the conventional hydrogen storage alloys described above, the hydrogen dissociation pressure at room temperature is 2 atm or more, making it difficult to electrochemically store sufficient hydrogen at normal pressure. I couldn't say it was on target.
（Ｊ題を解決する為の手段）
本発明は、常圧で充分な水素を吸蔵し得るとともに放電
容量の大きな新規な水素吸蔵合金電極を得ることを目的
とし、水素吸蔵合金電極として、Ｚ ｒ ｌ−Ｘ Ｔ
ｉｘ （Ｖｌｌ、３３Ｎ ｉ ｏ、ｈｔ） ｔ＋＋７
％但し、０≦Ｘ≦０．２．０≦Ｙ５１、の一般式で表
される合金又はその水素化物からなることを特徴とする
ものである。(Means for Solving Problem J) The purpose of the present invention is to obtain a novel hydrogen storage alloy electrode that can store sufficient hydrogen at normal pressure and has a large discharge capacity. l-X T
ix (Vll, 33N io, ht) t++7
% However, it is characterized by being made of an alloy represented by the general formula of 0≦X≦0.2.0≦Y51 or a hydride thereof.
（実施例）
以下本発明の実施例を詳細に説明すると、市販のジルコ
ニュウム、チタン、バナジウム、ニッケルの各粉末を所
定の組成比、例えばＺｒ（Ｖ。、、。(Example) Examples of the present invention will be described in detail below. Commercially available zirconium, titanium, vanadium, and nickel powders were mixed at a predetermined composition ratio, for example, Zr(V., . . . ).
Ｎ ｉ ｔｓ、 ｂ−Ｉ） ｔすなわちＺ ｒ Ｖ ｏ
、 ｈｑ Ｎ Ｉ ＋、 ＊ｘを得る場合はＺｒ：Ｖ：
Ｎｉを３＝２：４の組成比となる様に秤量混合し、これ
らをアーク溶解法により加熱溶解して水素吸蔵合金を得
、該合金を粗粉砕した後真空加熱装置で９００℃に加熱
し１気圧の水素を導入後室温迄冷却して合金の水素化と
活性化を行った。得られた水素化した合金をさらに粉砕
し４００メツシユ以下の微粉末とした。こうして得られ
た水素吸蔵合金微粉末を５ｔ／−で加圧成形し、直径ｌ
ｅａの円形ペレット状に形成した後、真空中９００℃で
焼結を行いこれにリード線を取り付けて水素吸蔵合金電
極とした。尚、電極中の水素吸蔵合金粉末の重量は約１
ｇである。N it's, b-I) t or Z r Vo
, hq N I +, *When obtaining x, Zr:V:
Ni was weighed and mixed to have a composition ratio of 3=2:4, and these were heated and melted using an arc melting method to obtain a hydrogen storage alloy.The alloy was coarsely ground and then heated to 900°C with a vacuum heating device. After introducing hydrogen at 1 atm, the alloy was cooled to room temperature to hydrogenate and activate the alloy. The obtained hydrogenated alloy was further ground into a fine powder of 400 mesh or less. The hydrogen storage alloy fine powder thus obtained was press-molded at 5t/-, and the diameter was l.
After forming the pellet into a circular pellet of ea, it was sintered at 900° C. in vacuum and a lead wire was attached to the pellet to obtain a hydrogen storage alloy electrode. The weight of the hydrogen storage alloy powder in the electrode is approximately 1
It is g.
この様にして種々の合金組成の水素吸蔵合金からなる電
極を作成し、得られた水素吸蔵合金電極を作用極としニ
ッケル板を対極として組合せ、アルカリ電解液として３
０ｗｔ％の水酸化カリウム水溶液を用いて開放型の試験
セルとした。試験セルの充電は６＋ｓＡ／−の電流密度
で水素吸蔵合金電極の電気化学的水素吸蔵量の１３０％
まで行った。In this way, electrodes made of hydrogen storage alloys with various alloy compositions were created, and the obtained hydrogen storage alloy electrodes were used as working electrodes and nickel plates were used as counter electrodes.
An open type test cell was prepared using a 0 wt % potassium hydroxide aqueous solution. The test cell was charged at a current density of 6+sA/- to 130% of the electrochemical hydrogen storage capacity of the hydrogen storage alloy electrode.
I went to
放電は、放１に電流１０ｍＡ／ｃｄで電圧が−０，７５
Ｖ ｖｓＨＲ／ ｕ、、ｏになるまで行った。このよう
な条件で充放電を繰り返し行い、水素吸蔵合金電極が活
性化する為に要した充放電サイクル数及び安定した状態
での放電容量を測定した。合金の各組成における放電容
量及び活性化の為の充放電サイクル数を第１表に示す。The discharge is at a current of 10 mA/cd and a voltage of -0.75.
The process was continued until V vsHR/u,,o. Charge and discharge were repeated under these conditions, and the number of charge and discharge cycles required to activate the hydrogen storage alloy electrode and the discharge capacity in a stable state were measured. Table 1 shows the discharge capacity and number of charge/discharge cycles for activation for each alloy composition.
第１表
＊１は「活性化の為の充放電゛サイクル数（回）」の欄
である。Table 1*1 is a column of "number of charge/discharge cycles for activation (times)".
この表からも明らかな如く、本発明による水素吸蔵合金
電極は、水素吸蔵合金電極として一般に要求される放電
容！２００ｍＡＨ／ＩＣを何れも上回り良好な結果を得
た。又、特に合金としてジルコニウムの１部をチタンで
置換したものは活性化の為の充放電サイクル数が１回で
あり、このことは１回の充電の後放電すれば所定の放電
容量が得られることを示し、ジルコニウムの１部をチタ
ンで置換することが活性化に効果があることが分かる。As is clear from this table, the hydrogen storage alloy electrode according to the present invention has a discharge capacity that is generally required for a hydrogen storage alloy electrode. Good results were obtained in all cases exceeding 200 mAH/IC. In addition, in particular, alloys in which part of the zirconium is replaced with titanium require only one charge/discharge cycle for activation, which means that a predetermined discharge capacity can be obtained by discharging after one charge. This shows that replacing a portion of zirconium with titanium is effective for activation.
しかしチタンの置換量が増えると放電容量が低下する為
、チタンの置換量はジルコニウムの組成比の０．２以下
にすべきである。However, as the amount of titanium substituted increases, the discharge capacity decreases, so the amount of titanium substituted should be 0.2 or less of the composition ratio of zirconium.
又、第１図は、Ｚ ｒ （Ｖｏ、３３Ｎ ｉ ｏ、ｂ、
） ｔ＋ｖに於けるＹの値と放電容量の関係を示すもの
である、縦軸は放電容量、横軸はＹの値を示す。この図
からも明らかな如く放電容ｔ ２００ｍＡＩ（／ Ｒを
満たすにはＹの値が１以下であることが必要である、さ
らにＹの値が１を越えた場合は水素解離圧が１気圧以上
となり容量が減少した。父上記チタンの各置換量に於い
ても同様にＹの値は１以下であることか必要である。In addition, FIG. 1 shows that Z r (Vo, 33N io, b,
) This shows the relationship between the value of Y and the discharge capacity at t+v. The vertical axis shows the discharge capacity, and the horizontal axis shows the value of Y. As is clear from this figure, in order to satisfy the discharge capacity t 200 mAI (/R), the value of Y must be less than 1, and if the value of Y exceeds 1, the hydrogen dissociation pressure must be more than 1 atm. As a result, the capacity decreased.For each of the above titanium substitution amounts, it is also necessary that the value of Y be 1 or less.
尚、本発明による合金を用いてこれを負極とし、正極と
して焼結基板に酸化ニッケルを含浸しでなる焼結ニッケ
ル極を用い、３０％の水酸化カリウム水溶液を電解液と
して円筒型密閉ニッケル水素電池を作成した場合もほぼ
同様に良好な結果が得られた。さらに、上記実施例では
焼結式の水素吸蔵合金電極を示したが、水素吸蔵合金の
微粉末を結着剤等で混練してペースト状としこれを集電
体等に塗布充填したペースト式電極等としても良い。The alloy according to the present invention was used as a negative electrode, a sintered nickel electrode made by impregnating a sintered substrate with nickel oxide was used as a positive electrode, and a cylindrical sealed nickel-metal hydride electrode was used as an electrolyte with a 30% potassium hydroxide aqueous solution. Almost the same good results were obtained when batteries were made. Furthermore, although the above example shows a sintered hydrogen storage alloy electrode, a paste type electrode is obtained by kneading fine powder of a hydrogen storage alloy with a binder or the like to form a paste, which is then applied and filled onto a current collector, etc. etc. may also be used.
（発明の効果）
以上の遺り本発明によれば、水素吸蔵合金電極が一般式
、Ｚ ｒ Ｉ−Ｘ Ｔ ｉ １１ （Ｖｏ、ｔｔＮ
ｉ ｏ、ｈｒ）ｔｓｖ、但しＯ≦Ｘ≦０．２．０≦Ｙ≦
１、で表される水素吸蔵合金又はその水素化物からなる
ので、常圧で水素の吸蔵・放出をし得ると共に、高容量
で活性化の容易な水素吸蔵合金電極が得られる等の効果
を奏するものである。(Effects of the Invention) According to the present invention, the hydrogen storage alloy electrode has the general formula Z r I-X T i 11 (Vo, ttN
i o, hr) tsv, however, O≦X≦0.2.0≦Y≦
Since it is made of the hydrogen storage alloy represented by 1 or its hydride, it can store and release hydrogen at normal pressure, and has the advantage of being able to obtain a hydrogen storage alloy electrode with high capacity and easy activation. It is something.
？ＪＪ１図はＺｒ （■。、 ｘｓ Ｎ ｉ ６． ａｙ）に於ける Ｙの値と放電容量との関係図である。 ? JJ1 diagram is Zr (■., xs N i 6. ay) It is a relationship diagram between the value of Y and discharge capacity.
Claims (1)
０＿．＿６＿７）＿２＿＋＿Ｙ、但し０≦ｘ≦０．２、
０≦Ｙ≦１、 で表される水素吸蔵合金又はその水素化物からなる水素
吸蔵合金電極。[Claims] General formula Zr_1_-_xTi_x(V_0_._3_3Ni_
0__. ＿６＿７）＿２＿＋＿Y、However, 0≦x≦0.2,
A hydrogen storage alloy electrode made of a hydrogen storage alloy or its hydride represented by 0≦Y≦1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1040894A JP2537084B2 (en) | 1989-02-21 | 1989-02-21 | Hydrogen storage alloy electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1040894A JP2537084B2 (en) | 1989-02-21 | 1989-02-21 | Hydrogen storage alloy electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02220355A true JPH02220355A (en) | 1990-09-03 |
| JP2537084B2 JP2537084B2 (en) | 1996-09-25 |
Family
ID=12593218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1040894A Expired - Lifetime JP2537084B2 (en) | 1989-02-21 | 1989-02-21 | Hydrogen storage alloy electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2537084B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04176833A (en) * | 1990-11-09 | 1992-06-24 | Furukawa Battery Co Ltd:The | Hydrogen storage alloy electrode |
| EP0703633A1 (en) * | 1994-08-17 | 1996-03-27 | AT&T Corp. | Process for activation of metal hydrides |
| CN105039765A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing V-Ti-Cr-Fe hydrogen storage alloy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6145563A (en) * | 1984-04-16 | 1986-03-05 | エナ−ジ−・コンバ−シヨン・デバイセス・インコ−ポレ−テツド | Active substance for hydrogen storage electrode, method of forming same and electrochemical application |
| JPS6435863A (en) * | 1987-07-30 | 1989-02-06 | Matsushita Electric Industrial Co Ltd | Hydrogen absorbing electrode |
| JPS6460961A (en) * | 1987-08-31 | 1989-03-08 | Matsushita Electric Industrial Co Ltd | Hydrogen absorption electrode |
| JPH01165737A (en) * | 1987-11-17 | 1989-06-29 | Kuochih Hong | Hydrogen storing method and hydride electrode material |
-
1989
- 1989-02-21 JP JP1040894A patent/JP2537084B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6145563A (en) * | 1984-04-16 | 1986-03-05 | エナ−ジ−・コンバ−シヨン・デバイセス・インコ−ポレ−テツド | Active substance for hydrogen storage electrode, method of forming same and electrochemical application |
| JPS6435863A (en) * | 1987-07-30 | 1989-02-06 | Matsushita Electric Industrial Co Ltd | Hydrogen absorbing electrode |
| JPS6460961A (en) * | 1987-08-31 | 1989-03-08 | Matsushita Electric Industrial Co Ltd | Hydrogen absorption electrode |
| JPH01165737A (en) * | 1987-11-17 | 1989-06-29 | Kuochih Hong | Hydrogen storing method and hydride electrode material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04176833A (en) * | 1990-11-09 | 1992-06-24 | Furukawa Battery Co Ltd:The | Hydrogen storage alloy electrode |
| EP0703633A1 (en) * | 1994-08-17 | 1996-03-27 | AT&T Corp. | Process for activation of metal hydrides |
| US5560752A (en) * | 1994-08-17 | 1996-10-01 | Lucent Technologies Inc. | Process for activation of metal hydrides |
| CN105039765A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing V-Ti-Cr-Fe hydrogen storage alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2537084B2 (en) | 1996-09-25 |
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