JPH03241673A - Formation method for nickel-hydrogen storage battery - Google Patents
Formation method for nickel-hydrogen storage batteryInfo
- Publication number
- JPH03241673A JPH03241673A JP2037614A JP3761490A JPH03241673A JP H03241673 A JPH03241673 A JP H03241673A JP 2037614 A JP2037614 A JP 2037614A JP 3761490 A JP3761490 A JP 3761490A JP H03241673 A JPH03241673 A JP H03241673A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen storage
- nickel
- storage alloy
- negative electrode
- formation
- 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
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- 238000003860 storage Methods 0.000 title claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 12
- 229910003126 Zr–Ni Inorganic materials 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000018199 S phase Effects 0.000 description 1
- 229910008340 ZrNi Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003466 welding Methods 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/34—Gastight accumulators
- H01M10/345—Gastight metal hydride accumulators
-
- 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
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
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−水素蓄電池の化成法に関すも。[Detailed description of the invention] Industrial applications The present invention also relates to a method for forming a nickel-hydrogen storage battery.
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も 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
池は各種ポータプル機器用へ 大型は産業用として使わ
れてき九
このアルカリ蓄電池において、正極として８よほとんど
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
用途も広がっ九
一方負極としては現在のところカドミウム極が主体であ
る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。Conventional technology Lead-acid batteries and alkaline batteries are widely used as storage batteries for various power sources.Among these, alkaline storage batteries are expected to have high reliability, and small batteries are used for various portable devices because they can be made smaller and lighter. In large alkaline storage batteries, which are used for industrial purposes, the positive electrode is almost always a nickel electrode. The pocket type was replaced by the sintered type, which improved its properties, made it possible to seal it, and expanded its uses.On the other hand, the negative electrode is currently mainly made of cadmium, but in order to achieve even higher energy density. Nickel-hydrogen storage batteries that use metal hydrides, that is, hydrogen-absorbing alloy electrodes, have attracted attention and many proposals have been made for manufacturing methods.
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 繊維塊 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。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硬れ
ているので非焼結成極の可能性は大きい。すなわち結着
剤とともにペスト状としこれを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。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。とくに水素吸蔵合金とし
てＺｒ−ＮｉをベースとするＡＢ２Ｌａｖｅｓ相を含む
合金では最終的には高容量になるが初期の活性化が問題
である。Problems to be Solved by the Invention Methods for producing hydrogen storage alloy electrodes include a method of sintering alloy powder and a paste method of filling or coating a porous body such as a foamed fiber mass or punched metal. Hydrogen storage alloys, like cadmium electrodes, are relatively hard in terms of electronic conductivity, so there is a strong possibility that they will be non-sintered electrodes. That is, it is made into a paste together with a binder and is filled or applied to a porous conductive plate having a three-dimensional or two-dimensional structure. However, in any case, there is room for improvement, especially in terms of discharge characteristics at the beginning of the charge/discharge cycle. In particular, an alloy containing an AB2Laves phase based on Zr-Ni as a hydrogen storage alloy ultimately has a high capacity, but initial activation is a problem.
課題を解決するための手段
本発明（よ ニッケル正極と水素吸蔵合金負極と前記ニ
ッケル正極と前記水素吸蔵合金負極を分離するセパレー
タとを電槽に挿入し 前記電槽に電解液を注入し 充電
のみからなる化成を行なうことを特徴とするニッケル−
水素蓄電池の化成法により上記課題を解決するものであ
る。Means for Solving the Problems According to the present invention (1) A nickel positive electrode, a hydrogen storage alloy negative electrode, and a separator for separating the nickel positive electrode and the hydrogen storage alloy negative electrode are inserted into a battery case, and an electrolyte is poured into the battery case, and only charging is performed. Nickel characterized by undergoing a chemical conversion consisting of
The above problem is solved by a chemical formation method for hydrogen storage batteries.
また ０〜１０℃程度の低温で充電することを特徴とす
る。It is also characterized by charging at a low temperature of about 0 to 10 degrees Celsius.
さら１ 負極に使用する水素吸蔵合金をＺｒＮｉをベー
スとするＡＢ２Ｌａｖｅｓ相を含む合金とすることを特
徴とする。Furthermore, the present invention is characterized in that the hydrogen storage alloy used for the negative electrode is an alloy containing an AB2Laves phase based on ZrNi.
作用
緩充電によることなく、−時に大充電化成して杖 上記
構成の合金は化成において、放電させなくとも水素を吸
蔵する能力と水素と酸素とを水に戻す触媒能は初期から
持っているので、充電により電池内圧が上昇してガス漏
れなどが生ずることはなｌ、％
な叙 この化成としての充電はＯ〜１０℃程度の低温で
あるほうが水素吸蔵合金の充電効率は良好である。The alloy with the above structure has the ability to absorb hydrogen without discharging and the catalytic ability to return hydrogen and oxygen to water from the beginning during chemical formation, without the need for slow charging. Charging does not increase the internal pressure of the battery and cause gas leakage, etc., and the charging efficiency of the hydrogen storage alloy is better when this chemical charging is performed at a low temperature of about 0 to 10°C.
実施例
水素吸蔵合金粉末をとくにＺｒ−ＮｉをベースとするＡ
ＢａＬａｖｅｓ相を含む合金は最終的には高容量になる
が初期の容量が少なｔ、％ そこで化成が他の電池系
以上に重要である。Examples Hydrogen storage alloy powders, especially Zr-Ni based A
Alloys containing the BaLaves phase ultimately have a high capacity, but the initial capacity is low (t,%).Therefore, chemical formation is more important than in other battery systems.
ところが一般の電池同様化成として緩充放電を繰り返す
と容量の増加の度合に比較的多くの充放電サイクルを必
要とした
それが本発明の放電を省略して充電のみにししかも好ま
しくは低温で負極容量の５倍以上のような大容量充電す
ることで改良が図られる。However, when slow charging and discharging are repeated as in general batteries, a relatively large number of charging and discharging cycles are required to increase the capacity.However, in the present invention, discharging is omitted and only charging is performed, and the negative electrode capacity is preferably increased at low temperatures. Improvements can be made by charging at a large capacity, such as 5 times or more.
な叙 かかる場合、合金が電極として機能するためには
充電での電極から水素が発生する状態を長く保つほど効
果的である。さらに他の電池同様に正極律則の電池構成
にしていて耘 負極の容量が不十分な化成時に放電を入
れると負極律則になるので責の電位になり、合金にとっ
て好ましくない酸化などを受けやすくなる。In such a case, in order for the alloy to function as an electrode, the longer the state in which hydrogen is generated from the electrode during charging is maintained, the more effective it is. Furthermore, like other batteries, the battery configuration is based on the positive electrode principle.If a discharge is applied during formation when the capacity of the negative electrode is insufficient, the negative electrode becomes a negative electrode principle, resulting in a negative potential, making it susceptible to oxidation, etc., which is unfavorable for the alloy. Become.
以上の理由で他の電池で（よ むしろ重要な化成時での
放電を本願発明のニッケル−水素系電池では入れない方
が化成が簡易化できてその上酸化も受けないので長寿命
になるという知見を得たな叙 他の蓄電池の場合密閉に
して負極から水素を発生させると触媒でも用いていなけ
れば水素は吸収されないので電池内圧は上昇してしまう
。For the above reasons, in other batteries (rather than in the nickel-metal hydride battery of the present invention), it is better to avoid discharging during the important chemical formation process, as the chemical formation can be simplified, and it will not undergo oxidation, resulting in a longer life. In the case of other storage batteries, if the battery is sealed and hydrogen is generated from the negative electrode, the internal pressure of the battery will rise because the hydrogen will not be absorbed unless a catalyst is used.
ところが水素吸蔵合金とくにＺｒ−Ｎｉをベースとする
ＡＢ２Ｌａｖｅｓ相を含む合金は水素を吸蔵する能力と
水素と酸素とを水に戻す触媒能は初期から持っているの
で電池内圧が上昇してガス漏れなどが生ずることはなｔ
℃ この化成としての充電は０〜１０℃程度の低温であ
るほうが水素吸蔵合金の充電効率は良好であ４
次に具体的実施例について述べる。水素吸蔵合金として
ＡＢ２ＬａｖｅＳ相合金の一つであるＺｒＭ ｎ ａ、
ｅｃ ｒ ＠、２Ｎ ｉ １．ｔ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多孔
度９５％厚さ１． ０ｍｍの発泡状ニッケル板に充填し
加圧して電極を得た 減圧で乾燥後５％のフッ素樹脂デ
ィスバージョンを添加し補強したこの電極を幅３３ｍｍ
、 長さ２１０ｍｍに裁断しリード板をスポット溶接
により取り付けた相手径として公知の発泡状ニッケル板
それに親木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九 正極に対
する負極の容量を４Ａｈ（１４０％）とじ九その後比重
１．２５の苛性カリ水溶液に２５ｇ／ｌの水酸化リチウ
ムを溶解した電解液を注入した電池は５ｕｂＣ形とした
公称容量は２．８Ａｈである。However, hydrogen storage alloys, especially alloys containing AB2Laves phase based on Zr-Ni, have the ability to store hydrogen and the catalytic ability to return hydrogen and oxygen to water from the beginning, so the internal pressure of the battery increases and gas leaks occur. will not occur.
C. The charging efficiency of the hydrogen storage alloy is better when the charging temperature is as low as about 0 to 10.degree. C.4.Next, specific examples will be described. ZrM na, which is one of the AB2Lave S phase alloys as a hydrogen storage alloy,
ec r @, 2N i 1. A paste made by adding a carboxymethylcellulose solution after crushing T.T. has a porosity of 95% and a thickness of 1. An electrode was obtained by filling a 0 mm foamed nickel plate and applying pressure. After drying under reduced pressure, this electrode was reinforced by adding 5% fluororesin dispersion to a width of 33 mm.
A sealed nickel-metal hydride storage battery was constructed using a well-known foamed nickel plate cut to a length of 210 mm and a lead plate attached to it by spot welding, and a parent-treated polypropylene nonwoven fabric separator. A 4Ah (140%) battery was injected with an electrolyte in which 25g/l of lithium hydroxide was dissolved in a caustic potassium aqueous solution with a specific gravity of 1.25.The battery had a nominal capacity of 2.8Ah.
この電池１０セルを用いて雰囲気温度１０℃のもとで化
成として４００ｍＡの電流で８０時間充電を行った こ
の電池をＡとする。This battery, in which 10 cells of this battery were used and charged for 80 hours with a current of 400 mA at an ambient temperature of 10° C., is designated as A.
つぎに比較のために従来の化成法の一例として室温２０
℃のもと２００ｍＡで２１時間（公称容量の１５０％）
充電−２００ｍＡで端子電圧０゜８ｖまでの放電の繰り
返しを行った電池を加えＢとした
化成後の放電電圧と容量を調べたところＡは平均電圧は
１．２０Ｖであり、放電容量は２０．８〜２．９Ａｈで
あっ九 ところがＢで（よ この特性を示すまでに７〜
１０サイクルを必要としたつぎに両型池それぞれ１０セ
ル用い４００ｍＡで１３０％充電−ＩＡで０．８ｖまで
の放電の充放電条件で寿命特性を比較した その結果放
電容量はＡでは１００−０サイクルでも初期の８０〜８
５％を示しているのに対してＢでは７０〜７５％であり
Ａの性能が長期にわたって安定してい九なお実施例では
密閉形について述べた力丈 開放形でも同じ効果がある
。Next, for comparison, as an example of a conventional chemical conversion method,
21 hours at 200 mA at °C (150% of nominal capacity)
A battery that had been repeatedly discharged at -200mA until the terminal voltage reached 0°8V was added to form B, and the discharge voltage and capacity after formation were investigated.A had an average voltage of 1.20V and a discharge capacity of 20. However, it took 7 to 2.9 Ah for B to show this characteristic.
Next, using 10 cells of both types of batteries, we compared the life characteristics under the charge/discharge conditions of 130% charging at 400 mA and discharging to 0.8 V with IA.As a result, the discharge capacity was 100-0 cycles for A. But the early 80-8
5%, whereas in B it is 70 to 75%, indicating that the performance of A is stable over a long period of time.In addition, in the embodiment, the force length described for the closed type has the same effect with the open type.
発明の効果
ニッケル正極と水素吸蔵合金負極とセパレータを用いて
電池を構成し電解液を注入後に充電のみからなる化成を
行なり＼ 正極容量律則にしてから用いることにより化
成の簡易化が可能となって充放電の初期から優れた特性
を示し これを長期にわたって維持できる。Effects of the Invention By constructing a battery using a nickel positive electrode, a hydrogen storage alloy negative electrode, and a separator, and performing chemical formation consisting only of charging after injecting an electrolyte, the chemical formation can be simplified by using the positive electrode capacity rule. It exhibits excellent characteristics from the beginning of charging and discharging, and can maintain this for a long period of time.
Claims (5)
正極と前記水素吸蔵合金負極を分離するセパレータとを
電槽に挿入し、前記電槽に電解液を注入し、充電のみか
らなる化成を行なうことを特徴とするニッケル−水素蓄
電池の化成法。(1) Inserting a nickel positive electrode, a hydrogen storage alloy negative electrode, and a separator that separates the nickel positive electrode and hydrogen storage alloy negative electrode into a battery case, pouring an electrolyte into the battery case, and performing chemical formation consisting only of charging. A chemical formation method for nickel-hydrogen storage batteries characterized by:
らなる化成を行なうことを特徴とする請求項１記載のニ
ッケル−水素蓄電池の化成法。(2) The method for forming a nickel-hydrogen storage battery according to claim 1, characterized in that after injecting the electrolytic solution, the cell is made into a sealed type, and then the forming process consists only of charging.
請求項１または２に記載のニッケル−水素蓄電池の化成
法。(3) The method for forming a nickel-hydrogen storage battery according to claim 1 or 2, wherein charging is performed at a low temperature around 0°C.
取り出せる容量の５倍以上である請求項１記載のニッケ
ル−水素蓄電池の化成法。(4) The method for forming a nickel-hydrogen storage battery according to claim 1, wherein the amount of electricity charged during forming is five times or more the capacity that can actually be extracted from the hydrogen storage alloy negative electrode.
ＡＢ＿２Ｌａｖｅｓ相を含む請求項１記載のニッケル−
水素蓄電池の化成法。(5) The nickel-based hydrogen storage alloy according to claim 1, wherein the hydrogen storage alloy contains an AB_2Laves phase based on Zr-Ni.
Chemical synthesis method for hydrogen storage batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2037614A JPH03241673A (en) | 1990-02-19 | 1990-02-19 | Formation method for nickel-hydrogen storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2037614A JPH03241673A (en) | 1990-02-19 | 1990-02-19 | Formation method for nickel-hydrogen storage battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03241673A true JPH03241673A (en) | 1991-10-28 |
Family
ID=12502496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2037614A Pending JPH03241673A (en) | 1990-02-19 | 1990-02-19 | Formation method for nickel-hydrogen storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03241673A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696825A1 (en) | 1994-08-09 | 1996-02-14 | Japan Storage Battery Company Limited | Method for manufacturing nickel-metal-hydride battery |
-
1990
- 1990-02-19 JP JP2037614A patent/JPH03241673A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0696825A1 (en) | 1994-08-09 | 1996-02-14 | Japan Storage Battery Company Limited | Method for manufacturing nickel-metal-hydride battery |
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