JPH0766804B2 - Manufacturing method of hydrogen storage alloy electrode for alkaline battery - Google Patents
Manufacturing method of hydrogen storage alloy electrode for alkaline batteryInfo
- Publication number
- JPH0766804B2 JPH0766804B2 JP1305448A JP30544889A JPH0766804B2 JP H0766804 B2 JPH0766804 B2 JP H0766804B2 JP 1305448 A JP1305448 A JP 1305448A JP 30544889 A JP30544889 A JP 30544889A JP H0766804 B2 JPH0766804 B2 JP H0766804B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- storage alloy
- hydrogen
- electrode
- alkaline battery
- 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
Links
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 39
- 239000001257 hydrogen Substances 0.000 title claims description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 35
- 229910045601 alloy Inorganic materials 0.000 title claims description 27
- 239000000956 alloy Substances 0.000 title claims description 27
- 238000003860 storage Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910003126 Zr–Ni Inorganic materials 0.000 claims description 3
- 229910001068 laves phase Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 238000011109 contamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/242—Hydrogen storage electrodes
-
- 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)
Description
【発明の詳細な説明】 産業上の利用分野 本発明はニッケル−水素蓄電池用などの水素吸蔵合金極
に関する。TECHNICAL FIELD The present invention relates to a hydrogen storage alloy electrode for nickel-hydrogen storage batteries and the like.
従来の技術 各種の電源として広く使われている蓄電池として鉛電池
とアルカリ電池がある。このうちアルカリ蓄電池は高信
頼性が期待でき、小形軽量化も可能などの理由で小型電
池は各種ポータブル機器用に、大型は産業用として使わ
れてきた。2. Description of the Related Art Lead batteries and alkaline batteries are widely used as storage batteries for various power sources. Among them, the alkaline storage battery can be expected to have high reliability and can be made compact and lightweight. For this reason, the small battery has been used for various portable devices and the large battery for industrial use.
このアルカリ蓄電池において、正極としては一部空気極
なども取り上げられているが、ほとんどの場合ニッケル
極である。ポケット式から焼結式に代わって特性が向上
し、さらに密閉化が可能になるとともに用途も広がっ
た。In this alkaline storage battery, an air electrode or the like is also taken up as a positive electrode, but in most cases, it is a nickel electrode. The characteristics have been improved from the pocket type to the sintered type, and it has become possible to further seal and expand the applications.
一方、負極としてはカドミウムの他に亜鉛、鉄、水素な
どが対象となっている。しかし現在のところカドミウム
極が主体である。ところが一層の高エネルギー密度を達
成するために金属水素化物つまり水素吸蔵合金極を使っ
たニッケル−水素蓄電池が注目され製法などに多くの提
案がされている。On the other hand, as the negative electrode, in addition to cadmium, zinc, iron, hydrogen, etc. are targeted. However, at present, the cadmium pole is the main one. However, in order to achieve a higher energy density, a nickel-hydrogen storage battery using a metal hydride, that is, a hydrogen storage alloy electrode has received attention, and many proposals have been made for its manufacturing method.
発明が解決しようとする課題 水素吸蔵合金極の製法としては合金粉末を焼結する方式
と発泡状、繊維状、パンチングメタルなどの多孔体に充
填や塗着する方式のペースト式がある。このうち製法が
簡単なのがペースト式である。水素吸蔵合金はカドミウ
ム極などと同様に電子伝導性の点で比較的優れているの
で非焼結式極の可能性は大きい。すなわち結着剤ととも
にペースト状としこれを３次元あるいは２次元構造の多
孔性導電板に充填あるいは塗着している。この場合結着
剤としてポリビニルアルコールやカルボキシメチルセル
ロースなどのイオン透過性樹脂やスチレン系ゴムなどが
用いられる。しかし、いずれにしてもとくに充放電サイ
クルの初期での放電特性の上で改良の余地がある。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As a method for manufacturing a hydrogen storage alloy electrode, there are a paste method of sintering an alloy powder and a method of filling or coating a porous body such as foam, fibrous or punching metal. Of these, the paste method is the easiest to manufacture. Since hydrogen storage alloys are relatively excellent in electron conductivity in the same manner as cadmium electrodes, the possibility of non-sintered electrodes is great. That is, it is made into a paste together with a binder and is filled or coated on a porous conductive plate having a three-dimensional or two-dimensional structure. In this case, an ion-permeable resin such as polyvinyl alcohol or carboxymethyl cellulose or styrene rubber is used as the binder. However, in any case, there is room for improvement, especially in the discharge characteristics at the beginning of the charge / discharge cycle.
課題を解決するための手段 水素吸蔵合金に結着剤溶液を加えて混合しペースト状の
液とし、この後このペーストに高圧の水素を加えての吸
蔵と高温や減圧による放出を少なくとも１回繰り返しこ
れを用いて電極を製造する。また、この場合負極に使用
する水素吸蔵合金が特にZr−NiをベースとするAB2Laves
相を含むことが好ましい。さらに、このペースト状を多
孔性導電板に充填したり塗着することを特徴とする。Means for Solving the Problems A binder solution is added to a hydrogen-absorbing alloy and mixed to form a paste-like liquid. After that, high-pressure hydrogen is added to this paste to absorb it and release it at high temperature or reduced pressure at least once. An electrode is manufactured using this. Further, in this case, the hydrogen storage alloy used for the negative electrode is AB 2 Laves based on Zr-Ni in particular.
It is preferable to include a phase. Further, it is characterized in that the paste is filled or coated on the porous conductive plate.
作用 水素吸蔵合金粉末を水素中などで焼結する方式に比べる
とペーストを発泡状や繊維状の多孔体、バンチングメタ
ルなどにに充填する方式は当然電子伝導性がない結着剤
との接触の比率が大きい。このことから合金の表面の酸
化などの汚染に留意することが必要である。水素吸蔵合
金は極めて活性であるから空気に瞬時でも触れると酸化
を受ける。ところが本願ではペーストにしてから水素を
供給して吸蔵し、これを放出させるので合金が水素と反
応してからは直接大気に触れることがなく汚染の度合は
大いに減少させ得る。Action Compared with the method of sintering hydrogen-absorbing alloy powder in hydrogen, etc., the method of filling the paste into a foamed or fibrous porous body or bunching metal naturally causes no contact with a binder that does not have electron conductivity. The ratio is large. Therefore, it is necessary to pay attention to contamination such as oxidation of the alloy surface. Hydrogen storage alloys are extremely active, so even if they are exposed to air, they will be oxidized. However, in the present application, since hydrogen is supplied after it is made into a paste to occlude it and release it, the alloy does not come into direct contact with the atmosphere after the reaction with hydrogen, and the degree of pollution can be greatly reduced.
なお、上記構成においては、ペーストにする前に水素の
吸蔵放出を行なう場合よりも水素が液中を通って合金に
到ることが必要なので吸蔵放出の面で、水素との反応性
に優れた特にZr−NiをベースとするAB2Laves相を含む合
金が適している。In the above structure, since it is necessary for hydrogen to pass through the liquid and reach the alloy as compared with the case where hydrogen is absorbed and released before forming a paste, the reactivity with hydrogen is excellent in terms of absorption and desorption. Particularly suitable are alloys containing the AB 2 Laves phase based on Zr-Ni.
実施例 水素吸蔵合金としてAB2Laves相合金の一つであるZrMn
0.6Cr0.2Ni1.2を粉砕した後カルボキシメチルセルロー
ス溶液を加えて作ったペーストを水素ガスの導入が可能
な密閉可能な圧力容器に入れ、この容器内を真空減圧し
た後30Kg/cm2の圧力で水素を供給する。水素吸蔵合金は
ペースト化しているが、水素吸蔵がゆっくりと進行す
る。充分水素吸蔵が行えたことを確認し、今度は容器内
の水素圧力を減圧し、水素の放出を行なう。この吸蔵放
出の操作を３回繰り返す。Example ZrMn which is one of AB 2 Laves phase alloys as a hydrogen storage alloy
0.6 Cr 0.2 Ni 1.2 was crushed and then a paste made by adding carboxymethyl cellulose solution was placed in a pressure vessel capable of introducing hydrogen gas, and after depressurizing the vessel in vacuum, hydrogen was added at a pressure of 30 kg / cm2. Supply. Although the hydrogen storage alloy is made into a paste, hydrogen storage progresses slowly. After confirming that hydrogen was sufficiently absorbed, the hydrogen pressure inside the container was reduced to release hydrogen. This operation of occluding and releasing is repeated three times.
ついでこのペーストを多孔度95％厚さ0.8mmの発泡状ニ
ッケル板に充填し加圧して容量密度1600mAh/ccの電極を
得た。減圧で乾燥後５％のフッ素樹脂ディスパージョン
を添加し補強した。得られた発泡状ペースト式水素吸蔵
合金極を幅33mm、長さ210mmに裁断し、リード板をスポ
ット溶接により取り付けた。Then, this paste was filled in a foamed nickel plate having a porosity of 95% and a thickness of 0.8 mm and pressed to obtain an electrode having a capacity density of 1600 mAh / cc. After drying under reduced pressure, 5% fluororesin dispersion was added to reinforce. The obtained foamed paste type hydrogen storage alloy electrode was cut into a width of 33 mm and a length of 210 mm, and a lead plate was attached by spot welding.
相手極として公知の発泡状ニッケル極、それに親水処理
ポリプロピレン不織布セパレータを用いて密閉形ニッケ
ル−水素蓄電池を構成した。電解液として比重1.25の苛
性カリ水溶液に15g/1の水酸化リチウムを溶解して用い
た。電池はsubC形とした。正極に対する負極の計算容量
を180％とした。この電池をＡとする。A sealed nickel-hydrogen storage battery was constructed using a known foamed nickel electrode as a counter electrode and a hydrophilically treated polypropylene nonwoven fabric separator. As an electrolytic solution, 15 g / 1 lithium hydroxide was dissolved in a caustic potash aqueous solution having a specific gravity of 1.25 and used. The battery was a sub C type. The calculated capacity of the negative electrode with respect to the positive electrode was set to 180%. This battery is designated as A.
つぎに、比較のために合金を粉砕後、ただちにＡと同じ
結着剤を用いてペースト化し、水素ガスでの水素吸蔵と
水素放出の工程だけを行わず他はＡと同じ工程で得られ
た電池をＢとして加えた。Then, for comparison, the alloy was crushed and immediately formed into a paste using the same binder as A, and the steps other than the steps of hydrogen absorption and desorption with hydrogen gas were not performed, and the other steps were obtained in the same step as A. Batteries were added as B.
まず初期の放電電圧と容量を比較した。５時間率で容量
の130％定電流充電−1.0Aで0.9Vまでの定電流放電を行
なったところ、Ａは平均電圧は1.20Vであり、放電容量
は２サイクル以後ほぼ一定で2.7〜2.8Ahであった。First, the initial discharge voltage and capacity were compared. When constant current charge of 130% of capacity at 5-hour rate and constant current discharge of up to 0.9V was performed at 1.0A, A had an average voltage of 1.20V, and the discharge capacity was almost constant after 2 cycles of 2.7 to 2.8Ah. Met.
ところがＢでは、特性が向上してほぼ一定になるまでに
８〜15サイクルを必要としその後はＡとほぼ同じ放電容
量を示した。However, in B, 8 to 15 cycles were required until the characteristics improved and became almost constant, and thereafter, the discharge capacity showed almost the same as A.
つぎに両電池それぞれ10セル用い、この充放電の条件で
寿命特性を比較した。その結果、Ａでは500サイクルで
も初期の90％以上の放電容量を示しているのに対して、
Ｂでは500サイクルでは75％以下であった。この結果か
ら明らかなようにＡが長寿命であった。Next, 10 cells were used for each battery, and the life characteristics were compared under the conditions of this charge / discharge. As a result, in A, the discharge capacity was 90% or more of the initial value even after 500 cycles, whereas
In B, it was 75% or less at 500 cycles. As is clear from this result, A had a long life.
発明の効果 水素吸蔵合金に結着剤溶液を加えて混合しペースト状に
し、その後このペーストに水素を加えての吸蔵と放出を
少なくとも１回以上繰り返しこれを用いて電極を製造す
ることにより特性の向上と長寿命が達成できる。Effects of the Invention A binder solution is added to a hydrogen storage alloy to mix them to form a paste, and then hydrogen is added to this paste to absorb and release hydrogen at least once, and an electrode is manufactured by using this to obtain the characteristics. Improvement and long life can be achieved.
Claims (5)
ペースト状にし、その後このペーストに水素を加えての
吸蔵と放出を少なくとも１回以上繰り返しこれを用いて
電極を製造することを特徴とするアルカリ電池用水素吸
蔵合金極の製造法。1. A hydrogen storage alloy is added with a binder solution and mixed to form a paste, and then hydrogen is added to this paste to absorb and release hydrogen at least once, thereby producing an electrode. A method of manufacturing a hydrogen storage alloy electrode for an alkaline battery, which is characterized.
をベースとするAB2Laves相を含む請求項１記載のアルカ
リ電池用水素吸蔵合金極の製造法。2. The hydrogen storage alloy used for the negative electrode is especially Zr-Ni.
The method for producing a hydrogen storage alloy electrode for an alkaline battery according to claim 1, which contains an AB 2 Laves phase based on Al.
造の多孔性導電体を用いた請求項１記載のアルカリ電池
用水素吸蔵合金極の製造法。3. The method for producing a hydrogen storage alloy electrode for an alkaline battery according to claim 1, wherein a porous conductor having a three-dimensional structure such as foam or felt is used for the support.
メタル、スクリーンなど２次元構造の多孔性導電体を用
いた請求項１記載のアルカリ電池用水素吸蔵合金極の製
造法。4. The method for producing a hydrogen storage alloy electrode for an alkaline battery according to claim 1, wherein a porous conductor having a two-dimensional structure such as punching metal, expanded metal or screen is used as the support.
を添加することを特徴とするアルカリ電池用水素吸蔵合
金極の製造法。5. A method for producing a hydrogen storage alloy electrode for an alkaline battery, which comprises adding a fluororesin dispersion after forming an electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1305448A JPH0766804B2 (en) | 1989-11-24 | 1989-11-24 | Manufacturing method of hydrogen storage alloy electrode for alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1305448A JPH0766804B2 (en) | 1989-11-24 | 1989-11-24 | Manufacturing method of hydrogen storage alloy electrode for alkaline battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03165462A JPH03165462A (en) | 1991-07-17 |
| JPH0766804B2 true JPH0766804B2 (en) | 1995-07-19 |
Family
ID=17945265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1305448A Expired - Lifetime JPH0766804B2 (en) | 1989-11-24 | 1989-11-24 | Manufacturing method of hydrogen storage alloy electrode for alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0766804B2 (en) |
-
1989
- 1989-11-24 JP JP1305448A patent/JPH0766804B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03165462A (en) | 1991-07-17 |
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