JPH063740B2 - Nickel-hydrogen secondary battery - Google Patents
Nickel-hydrogen secondary batteryInfo
- Publication number
- JPH063740B2 JPH063740B2 JP60257004A JP25700485A JPH063740B2 JP H063740 B2 JPH063740 B2 JP H063740B2 JP 60257004 A JP60257004 A JP 60257004A JP 25700485 A JP25700485 A JP 25700485A JP H063740 B2 JPH063740 B2 JP H063740B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- hydrogen storage
- storage alloy
- battery
- 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.)
- Expired - Lifetime
Links
- 239000001257 hydrogen Substances 0.000 title claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000956 alloy Substances 0.000 claims description 25
- 229910045601 alloy Inorganic materials 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- -1 silver ions Chemical class 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000008151 electrolyte solution Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 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
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)
Description
【発明の詳細な説明】 (イ) 産業上の利用分野 本発明は水素を吸蔵及び放出することのできる水素吸蔵
合金を備えた水素吸蔵合金負極と、ニッケル正極と、ア
ルカリ電解液とを備えたニッケル−水素二次電池に関す
る。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention includes a hydrogen storage alloy negative electrode provided with a hydrogen storage alloy capable of storing and releasing hydrogen, a nickel positive electrode, and an alkaline electrolyte. The present invention relates to a nickel-hydrogen secondary battery.
(ロ) 従来の技術 従来からよく用いられる二次電池としては、鉛電池、ニ
ッケル−カドミウム電池があるが、近年これら電池より
軽量で且つ高容量となる可能性があるということで、特
に低圧に於いて活物質である水素を可逆的に吸蔵及び放
出することのできる水素吸蔵合金を備えた電極を負極に
用い、水酸化ニッケルからなる活物質を備えた電極を正
極に用いたニッケル−水素二次電池が注目されている。(B) Conventional technology As a secondary battery that has been often used conventionally, there are a lead battery and a nickel-cadmium battery, but in recent years, there is a possibility that the battery is lighter and has a higher capacity. In the nickel-hydrogen battery, an electrode having a hydrogen storage alloy capable of reversibly storing and releasing hydrogen as an active material is used as a negative electrode, and an electrode having an active material made of nickel hydroxide is used as a positive electrode. Secondary batteries are receiving attention.
そして一般にこの種のニッケル−水素二次電池は、特公
昭５８−４６８２７号公報に於いて示されるように、水
素吸蔵合金負極とニッケル正極との間にセパレータを介
して構成され、充電時や保存時に正極から発生する酸素
ガスは充電状態の負極、すなわち負極中の水素吸蔵合金
に吸蔵した水素と反応して消費される構成となってい
る。ところが酸素は水素吸蔵合金中の水素と反応して水
になると共に、水素吸蔵合金と直接反応して水素吸蔵合
金の組成を化学的に変化させ、この化学変化によって水
素吸蔵合金は水素吸蔵能力を失い負極の容量が低下し、
長期にわたって高容量を維持することができず、また、
特に保存特性が悪かった。In general, a nickel-hydrogen secondary battery of this type is constituted by a separator between a hydrogen storage alloy negative electrode and a nickel positive electrode, as shown in Japanese Patent Publication No. 58-46827, and is charged or stored. Oxygen gas generated from the positive electrode is sometimes consumed by reacting with hydrogen stored in the charged negative electrode, that is, the hydrogen storage alloy in the negative electrode. However, oxygen reacts with hydrogen in the hydrogen storage alloy to become water, and directly reacts with the hydrogen storage alloy to chemically change the composition of the hydrogen storage alloy, and this chemical change causes the hydrogen storage alloy to have a hydrogen storage capacity. Loss of negative electrode capacity,
Unable to maintain high capacity for a long time, and
Especially the storage characteristics were poor.
(ハ) 発明が解決しようとする問題点 本発明は水素吸蔵合金負極を備えたニッケル−水素二次
電池の容量低下を抑制しようとするものである。(C) Problems to be Solved by the Invention The present invention is intended to suppress a decrease in capacity of a nickel-hydrogen secondary battery including a hydrogen storage alloy negative electrode.
(ニ) 問題点を解決するための手段 本発明のニッケル−水素二次電池は、水素吸蔵合金負極
とニッケル正極とを備え、アルカリ電解液中に銀イオ
ン、鉛イオン及び銅イオンから選ばれた少なくとも一種
の金属イオンを含有させたものである。(D) Means for Solving Problems The nickel-hydrogen secondary battery of the present invention comprises a hydrogen storage alloy negative electrode and a nickel positive electrode, and is selected from silver ions, lead ions and copper ions in an alkaline electrolyte. It contains at least one metal ion.
(ホ) 作用 アルカリ電解液中に含有させた銀イオン、鉛イオン及び
銅イオンから選ばれた少なくとも一種の金属イオンは、
ニッケル正極の酸素過電圧を高め、充電時及び放置時に
於ける正極からの酸素ガス発生を抑制し、水素吸蔵合金
負極中の水素が酸素と反応して容量低下することを抑制
でき、また水素吸蔵合金が酸素と反応して組成変化する
ことも抑制できる。(E) Action At least one metal ion selected from silver ions, lead ions and copper ions contained in the alkaline electrolyte,
Nickel Positive electrode Increases the oxygen overvoltage, suppresses the generation of oxygen gas from the positive electrode during charging and during storage, and can prevent hydrogen in the hydrogen storage alloy negative electrode from reacting with oxygen and decreasing in capacity, and also hydrogen storage alloy. Can also be suppressed from reacting with oxygen to change its composition.
(ヘ) 実施例 水素吸蔵能力を有するLaNi5を機械的に粉砕して微粉化
し、このLaNi5粉末に小さなせん断力で粒子が簡単に繊
維化し塑性変形するポリテトラフルオロエチレン粉末
を、LaNi5粉末の重量に対して１〜５％添加して混合機
で均一に混合すると共にポリテトラフルオロエチレンを
繊維化し、次いで水を加えてペースト状とする。その
後、このペーストをニッケルメッキを施したパンチグメ
タルからなる集電体に貼り付けて水素吸蔵合金負極を得
る。(F) Example LaNi 5 having a hydrogen storage capacity is mechanically pulverized into fine powder, and polytetrafluoroethylene powder in which particles are easily fiberized and plastically deformed by a small shearing force is added to this LaNi 5 powder, LaNi 5 powder 1 to 5% with respect to the weight of the above, and uniformly mixed with a mixer, and polytetrafluoroethylene is made into fibers, and then water is added to form a paste. Then, this paste is attached to a nickel-plated punched metal current collector to obtain a hydrogen storage alloy negative electrode.
また、水酸化ニッケル粉末にポリテトラフルオロエチレ
ン及び水を加えてペースト状とした後、このペーストを
ニッケルメッキを施したパンチングメタルからなる集電
体の両面に貼り付けてニッケル正極を得る。Further, polytetrafluoroethylene and water are added to nickel hydroxide powder to form a paste, and the paste is attached to both surfaces of a nickel-plated current collector made of punched metal to obtain a nickel positive electrode.
上記水素吸蔵合金負極とニッケル正極との間にセパレー
タを介挿し、これらを巻回して渦巻状の電極体を構成す
る。この電極体を電池外装缶に挿入した後水酸化カリウ
ム３０％、硫酸銅１％からなる電解液を注入し封口を行
なって本発明のニッケル−水素二次電池(A)を作製し
た。A separator is inserted between the hydrogen storage alloy negative electrode and the nickel positive electrode, and these are wound to form a spiral electrode body. This electrode body was inserted into a battery case, and then an electrolytic solution containing 30% potassium hydroxide and 1% copper sulfate was injected and sealed to prepare a nickel-hydrogen secondary battery (A) of the present invention.
また、同様にして電解液に水酸化カリウム３０％、酢酸
鉛0.5％からなる電解液を用いて電池(B)、水酸化カリウ
ム３０％、硫酸銀0.5％、アンモニア１％からなる電解
液を用いて電池(C)、水酸化カリウム３０％、硫酸銅１
％、酢酸鉛0.5％からなる電解液を用いて電池(D)を作製
すると共に、比較として水酸化カリウム３０％からなる
電解液を用いて電池(E)を作製した。Similarly, using an electrolytic solution containing 30% potassium hydroxide and 0.5% lead acetate as the electrolytic solution, a battery (B) using an electrolytic solution containing 30% potassium hydroxide, 0.5% silver sulfate and 1% ammonia. Battery (C), potassium hydroxide 30%, copper sulfate 1
%, And a battery (D) was prepared using an electrolytic solution containing 0.5% lead acetate, and a battery (E) was prepared using an electrolytic solution containing 30% potassium hydroxide for comparison.
これら本発明電池(A)乃至(D)及び比較電池(E)を１２０m
Aで１６時間充電し、次いで２４０mAで電池電圧が1.0Ｖ
になるまで放電する充放電サイクルを数回行なって初期
活性化を完了した後、１２０mAで１６時間充電して放置
時間と残存容量との関係を調べ、この結果を第１図に各
電池の初期容量を夫々１００として示した。尚、残存容
量は一定期間放置後に２４０mAで放電して測定したもの
である。また第２図は前記放置を１ケ月行なった後、電
池(A)乃至(E)を夫々前記充放電サイクルによって充放電
を繰り返し行なって測定したサイクル特性図である。Each of the batteries (A) to (D) of the present invention and the comparative battery (E) is 120 m
Charged at A for 16 hours, then at 240mA the battery voltage is 1.0V
After completing the initial activation by performing several charge / discharge cycles of discharging until the battery becomes full, it is charged at 120 mA for 16 hours and the relationship between the standing time and the remaining capacity is examined. The results are shown in FIG. The capacities are shown as 100 respectively. The remaining capacity is measured by discharging at 240 mA after standing for a certain period. Further, FIG. 2 is a cycle characteristic diagram measured by repeating charging / discharging of the batteries (A) to (E) by the charging / discharging cycle after left for one month.
これらの図面から明らかなように本発明電池(A)乃至(D)
は、比較電池(E)に比べて放置による容量の低下が小さ
く抑えられ、また放置後のサイクリ寿命が長く優れたも
のであることがわかる。また電池(D)より明らかな通り
電解液中に二種以上の前記金属イオンが含まれていても
同様の効果が表われている。As apparent from these drawings, the batteries of the present invention (A) to (D)
It can be seen that, compared with the comparative battery (E), the decrease in capacity due to leaving is suppressed to be small, and the cycle life after leaving is long and excellent. Further, as is apparent from the battery (D), the same effect is exhibited even when the electrolyte solution contains two or more kinds of the metal ions.
水素吸蔵合金負極は従来から用いられてきたカドミウム
負極とは異なり、満充電時には極めて活性であり、酸素
と接触すると非常に速い速度で反応して酸化する。そし
て、この酸化に於いて酸素は負極の水素吸蔵合金に吸蔵
された水素と反応して水になると共に水素吸蔵合金と反
応して水素吸蔵合金をしばしば組成の異なる他の物質に
変化させる。つまり、上記実施例に於いては放置した間
にLaNi5がLa2O3、La(OH)3、Ni、NiO、Ni(OH)2などに変
化することにより水素吸蔵能力を失い、以後充放電を繰
り返してもLaNi5に戻ることはない。Unlike the cadmium negative electrode that has been conventionally used, the hydrogen storage alloy negative electrode is extremely active when fully charged, and reacts and oxidizes at a very fast rate when contacted with oxygen. Then, in this oxidation, oxygen reacts with hydrogen stored in the hydrogen storage alloy of the negative electrode to become water, and also reacts with the hydrogen storage alloy to change the hydrogen storage alloy into another substance often having a different composition. That is, in the above example, LaNi 5 loses its hydrogen storage capacity by being changed to La 2 O 3 , La (OH) 3 , Ni, NiO, Ni (OH) 2 and the like while being left unattended. It does not return to LaNi 5 even after repeated discharge.
したがって比較電池(E)では正極から充電時に酸素が発
生し易いため充電後に電池内に酸素が多量に残存し、ま
た放置中にも正極から酸素が発生するので放置期間中の
容量低下が大きく、また負極の水素吸蔵合金の組成変化
も多く生じるため、放置後は充放電サイクルの経過に伴
う容量低下も大きくなっている。これに対して本発明電
池(A)乃至(D)では正極の酸素過電圧が電解液中に存在す
る銅イオン、鉛イオン、銀イオンによって高くなってい
るので、充電時及び放置時に於ける正極からの酸素ガス
発生が抑えられ容量の低下が小さい。また水素吸蔵合金
が酸素と反応することによる組成変化で水素吸蔵能力を
喪失することも抑えられるため、放置後のサイクル劣化
も少なくなっている。Therefore, in the comparative battery (E), oxygen is likely to be generated during charging from the positive electrode, so a large amount of oxygen remains in the battery after charging, and since oxygen is generated from the positive electrode even during standing, the capacity decrease during the standing period is large, In addition, since the composition of the hydrogen storage alloy of the negative electrode often changes, the capacity decreases greatly with the progress of the charging / discharging cycle after standing. On the other hand, in the batteries (A) to (D) of the present invention, the oxygen overvoltage of the positive electrode is increased by the copper ions, lead ions, and silver ions present in the electrolytic solution. Oxygen gas generation is suppressed and the decrease in capacity is small. Further, loss of hydrogen storage capacity due to a composition change caused by the reaction of the hydrogen storage alloy with oxygen can be suppressed, so that cycle deterioration after leaving is reduced.
尚、上記実施例では正極に非焼結式ニッケル正極を用い
て説明したが、公知の焼結式ニッケル正極を用いても同
様の効果を得ることができる。また実施例では負極の水
素吸蔵合金にLaNi5を用いたが、他の水素吸蔵合金を用
いた場合にも同様の効果が得られる。Although the non-sintered nickel positive electrode is used as the positive electrode in the above embodiment, the same effect can be obtained by using a known sintered nickel positive electrode. Although LaNi 5 was used as the hydrogen storage alloy of the negative electrode in the examples, the same effect can be obtained when other hydrogen storage alloys are used.
(ト) 発明の効果 本発明のニッケル−水素二次電池は水素吸蔵合金負極と
ニッケル正極と、銀イオン、鉛イオン及び銅イオンから
選ばれた少なくとも一種の金属イオンを含有したアルカ
リ電解液を備えたものであり、前記金属イオンによって
充電時及び放置時に於けるニッケル正極からの酸素ガス
発生を抑制することができ、負極が電池内で酸素と反応
することによる容量低下の抑制及び放置後のサイクル寿
命の向上を行なうことができる。(G) Effect of the invention The nickel-hydrogen secondary battery of the present invention comprises a hydrogen storage alloy negative electrode, a nickel positive electrode, and an alkaline electrolyte containing at least one metal ion selected from silver ions, lead ions and copper ions. The metal ions can suppress the generation of oxygen gas from the nickel positive electrode during charging and standing, and can suppress the capacity decrease due to the reaction of the negative electrode with oxygen in the battery and the cycle after standing. The life can be improved.
第１図は電池の放置日数と残存容量の関係を示す保存特
性図、第２図は１ケ月放置後のサイクル特性図である。 (A)〜(D)…本発明電池、(E)…比較電池。FIG. 1 is a storage characteristic diagram showing the relationship between the number of days the battery is left and the remaining capacity, and FIG. 2 is a cycle characteristic diagram after being left for one month. (A) to (D) ... Battery of the present invention, (E) ... Comparative battery.
Claims (1)
イオン、鉛イオン及び銅イオンから選ばれた少なくとも
一種の金属イオンを含有したアルカリ電解液を備えたニ
ッケル−水素二次電池。1. A nickel-hydrogen secondary battery comprising a nickel positive electrode, a hydrogen storage alloy negative electrode, and an alkaline electrolyte containing at least one metal ion selected from silver ions, lead ions and copper ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60257004A JPH063740B2 (en) | 1985-11-15 | 1985-11-15 | Nickel-hydrogen secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60257004A JPH063740B2 (en) | 1985-11-15 | 1985-11-15 | Nickel-hydrogen secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62117274A JPS62117274A (en) | 1987-05-28 |
| JPH063740B2 true JPH063740B2 (en) | 1994-01-12 |
Family
ID=17300384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60257004A Expired - Lifetime JPH063740B2 (en) | 1985-11-15 | 1985-11-15 | Nickel-hydrogen secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH063740B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3318141B2 (en) * | 1994-04-04 | 2002-08-26 | 松下電器産業株式会社 | Method for producing hydrogen storage alloy electrode |
-
1985
- 1985-11-15 JP JP60257004A patent/JPH063740B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62117274A (en) | 1987-05-28 |
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